Selective para-funtionalization of phenol
- Authors: Indurkar, Jayant R
- Date: 2008
- Subjects: Phenol
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10402 , http://hdl.handle.net/10948/710 , Phenol
- Description: In previous work done in our laboratories, a method was discovered to produce phenolic mono-ethers from 4-hydroxyacetophenone and other 4-hydroxyketones by treating with ammonium peroxy-disulfate in an alcohol as a reaction solvent and in the presence of concentrated sulphuric acid or other strong protonic acids. Since this method of producing 4-alkoxyphenol ethers provides a very convenient way to modify hydroquinone and substituted hydroquinones to produce a variety of phenol mono-ethers, it was of interest to study the general scope of this reaction, including a more detailed investigation of the reaction mechanism. In previous studies, it was suggested that interaction between the aromatic pi-system of hydroquinone and the cyclohexa-2,5-diene structure of benzoquinone plays a significant role during the reaction. It was therefore of interest to investigate whether other compounds that are also capable of forming the cyclohexa-2,5-diene structure, will interact in a manner analogous to the hydroquinone/benzoquinone couple. Two specific compounds were selected for this purpose, namely 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one . The scope of etherification reactions of hydroquinone-benzoquinone or hydroquinone/benzoquinone like substrates such as 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one in the presence of acid catalyst and alcohols was investigated. These studies showed that hydroquinone, 4- nitrosophenol and 4-(diphenylmethylene)cyclohexa-2,5-dien-1-one successfully affords the phenolic ethers in good to excellent yield. For example, quantitative yield of 4-methoxyphenol could be obtained from a 1:1 mixture of hydroquinone and benzoquinone at the reflux temperature of methanol. In order to study the reaction mechanism, the cross-over reaction between tertbutylhydroquinone and benzoquinone (or hydroquinone and tertbutylbenzoquinone) was studied in detail. The results of these cross-over reactions were used to propose a mechanistic pathway that could explain the requirement for pi-interaction between the hydroquinone and benzoquinone molecules, the role of the acid catalyst, as well as the relative rates of hydroquinone and benzoquinone consumption during these reactions. The mechanism was also capable of explaining all the reaction products observed during these reactions. The work was then extended to reactions of 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one with methanol in the presence of either hydroquinone or benzoquinone. The results of these investigations strongly suggest the presence of similar interactions between these molecules that also influence the outcome of the reactions. The exploitation of pi-interactions between two molecules of these types investigated during this work opens an interesting field of chemistry. Clearly, the level of understanding developed during this work is only beginning to address this interesting field of chemistry and much work will need to be done to gain a fuller understanding of the chemistry involved as well as the potential synthetic value of these interactions.
- Full Text:
- Date Issued: 2008
- Authors: Indurkar, Jayant R
- Date: 2008
- Subjects: Phenol
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10402 , http://hdl.handle.net/10948/710 , Phenol
- Description: In previous work done in our laboratories, a method was discovered to produce phenolic mono-ethers from 4-hydroxyacetophenone and other 4-hydroxyketones by treating with ammonium peroxy-disulfate in an alcohol as a reaction solvent and in the presence of concentrated sulphuric acid or other strong protonic acids. Since this method of producing 4-alkoxyphenol ethers provides a very convenient way to modify hydroquinone and substituted hydroquinones to produce a variety of phenol mono-ethers, it was of interest to study the general scope of this reaction, including a more detailed investigation of the reaction mechanism. In previous studies, it was suggested that interaction between the aromatic pi-system of hydroquinone and the cyclohexa-2,5-diene structure of benzoquinone plays a significant role during the reaction. It was therefore of interest to investigate whether other compounds that are also capable of forming the cyclohexa-2,5-diene structure, will interact in a manner analogous to the hydroquinone/benzoquinone couple. Two specific compounds were selected for this purpose, namely 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one . The scope of etherification reactions of hydroquinone-benzoquinone or hydroquinone/benzoquinone like substrates such as 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one in the presence of acid catalyst and alcohols was investigated. These studies showed that hydroquinone, 4- nitrosophenol and 4-(diphenylmethylene)cyclohexa-2,5-dien-1-one successfully affords the phenolic ethers in good to excellent yield. For example, quantitative yield of 4-methoxyphenol could be obtained from a 1:1 mixture of hydroquinone and benzoquinone at the reflux temperature of methanol. In order to study the reaction mechanism, the cross-over reaction between tertbutylhydroquinone and benzoquinone (or hydroquinone and tertbutylbenzoquinone) was studied in detail. The results of these cross-over reactions were used to propose a mechanistic pathway that could explain the requirement for pi-interaction between the hydroquinone and benzoquinone molecules, the role of the acid catalyst, as well as the relative rates of hydroquinone and benzoquinone consumption during these reactions. The mechanism was also capable of explaining all the reaction products observed during these reactions. The work was then extended to reactions of 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one with methanol in the presence of either hydroquinone or benzoquinone. The results of these investigations strongly suggest the presence of similar interactions between these molecules that also influence the outcome of the reactions. The exploitation of pi-interactions between two molecules of these types investigated during this work opens an interesting field of chemistry. Clearly, the level of understanding developed during this work is only beginning to address this interesting field of chemistry and much work will need to be done to gain a fuller understanding of the chemistry involved as well as the potential synthetic value of these interactions.
- Full Text:
- Date Issued: 2008
Solar cycle effects on GNSS-derived ionospheric total electron content observed over Southern Africa
- Authors: Moeketsi, Daniel Mojalefa
- Date: 2008
- Subjects: Ionosphere -- Africa, Southern Electrons Ionospheric electron density -- Africa, Southern Ionosondes -- Africa, Southern Electromagnetic waves
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5489 , http://hdl.handle.net/10962/d1005275
- Description: The South African Global Navigation Satellite System (GNSS) network of dual frequency receivers provide an opportunity to investigate solar cycle effects on ionospheric Total Electron Content (TEC) over the South Africa region by taking advantage of the dispersive nature of the ionospheric medium. For this task, the global University of New Brunswick Ionospheric Modelling Technique (UNB-IMT) was adopted, modified and applied to compute TEC using data from the southern African GNSS Network. TEC values were compared with CODE International GNSS services TEC predictions and Ionosonde-derived TEC (ITEC) measurements to test and validate the UNB-IMT results over South Africa. It was found that the variation trends of GTEC and ITEC over all stations are in good agreement and show pronounced seasonal variations with high TEC values around equinoxes for a year near solar maximum and less pronounced around solar minimum. Signature TEC depletions and enhanced spikes were prevalently evident around equinoxes, particularly for a year near solar maximum. These observations were investigated and further discussed with an analysis of the midday Disturbance Storm Time (DST) index of geomagnetic activity. The residual GTEC – ITEC corresponding to plasmaspheric electron content and equivalent ionospheric foF2 and total slab thickness parameters were computed and comprehensively discussed. The results verified the use of UNB-IMT as one of the tools for ionospheric research over South Africa. The UNB-IMT algorithm was applied to investigate TEC variability during different epochs of solar cycle 23. The results were investigated and further discussed by analyzing the GOES 8 and 10 satellites X-ray flux (0.1 – 0.8 nm) and SOHO Solar Extreme Ultraviolet Monitor higher resolution data. Comparison of UNB-IMT TEC derived from collocated HRAO and HARB GNSS receivers was undertaken for the solar X17 and X9 flare events, which occurred on day 301, 2003 and day 339, 2006. It was found that there exist considerable TEC differences between the two collocated receivers with some evidence of solar cycle dependence. Furthermore, the daytime UNB TEC compared with the International Reference Ionosphere 2001 predicted TEC found both models to show a good agreement. The UNB-IMT TEC was further applied to investigate the capabilities of geodetic Very Long Baseline Interferometry (VLBI) derived TEC using the Vienna TEC Model for space weather monitoring over HartRAO during the CONT02 and CONT05 campaigns conducted during the years 2002 (near solar maximum) and 005 (near solar minimum). The results verified the use of geodetic VLBI as one of the possible instruments for monitoring space weather impacts on the ionosphere over South Africa.
- Full Text:
- Date Issued: 2008
Solar cycle effects on GNSS-derived ionospheric total electron content observed over Southern Africa
- Authors: Moeketsi, Daniel Mojalefa
- Date: 2008
- Subjects: Ionosphere -- Africa, Southern Electrons Ionospheric electron density -- Africa, Southern Ionosondes -- Africa, Southern Electromagnetic waves
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5489 , http://hdl.handle.net/10962/d1005275
- Description: The South African Global Navigation Satellite System (GNSS) network of dual frequency receivers provide an opportunity to investigate solar cycle effects on ionospheric Total Electron Content (TEC) over the South Africa region by taking advantage of the dispersive nature of the ionospheric medium. For this task, the global University of New Brunswick Ionospheric Modelling Technique (UNB-IMT) was adopted, modified and applied to compute TEC using data from the southern African GNSS Network. TEC values were compared with CODE International GNSS services TEC predictions and Ionosonde-derived TEC (ITEC) measurements to test and validate the UNB-IMT results over South Africa. It was found that the variation trends of GTEC and ITEC over all stations are in good agreement and show pronounced seasonal variations with high TEC values around equinoxes for a year near solar maximum and less pronounced around solar minimum. Signature TEC depletions and enhanced spikes were prevalently evident around equinoxes, particularly for a year near solar maximum. These observations were investigated and further discussed with an analysis of the midday Disturbance Storm Time (DST) index of geomagnetic activity. The residual GTEC – ITEC corresponding to plasmaspheric electron content and equivalent ionospheric foF2 and total slab thickness parameters were computed and comprehensively discussed. The results verified the use of UNB-IMT as one of the tools for ionospheric research over South Africa. The UNB-IMT algorithm was applied to investigate TEC variability during different epochs of solar cycle 23. The results were investigated and further discussed by analyzing the GOES 8 and 10 satellites X-ray flux (0.1 – 0.8 nm) and SOHO Solar Extreme Ultraviolet Monitor higher resolution data. Comparison of UNB-IMT TEC derived from collocated HRAO and HARB GNSS receivers was undertaken for the solar X17 and X9 flare events, which occurred on day 301, 2003 and day 339, 2006. It was found that there exist considerable TEC differences between the two collocated receivers with some evidence of solar cycle dependence. Furthermore, the daytime UNB TEC compared with the International Reference Ionosphere 2001 predicted TEC found both models to show a good agreement. The UNB-IMT TEC was further applied to investigate the capabilities of geodetic Very Long Baseline Interferometry (VLBI) derived TEC using the Vienna TEC Model for space weather monitoring over HartRAO during the CONT02 and CONT05 campaigns conducted during the years 2002 (near solar maximum) and 005 (near solar minimum). The results verified the use of geodetic VLBI as one of the possible instruments for monitoring space weather impacts on the ionosphere over South Africa.
- Full Text:
- Date Issued: 2008
South Africa and Malaysia: identity and history in South-South relations
- Authors: Haron, Muhammed
- Date: 2008
- Subjects: Critical theory South Africa -- Foreign relations -- Malaysia Malaysia -- Foreign relations -- South Africa South Africa -- Politics and government -- History Malaysia -- Politics and government -- History South Africa -- Politics and government Malaysia -- Politics and government South Africa -- Social conditions -- History Malaysia -- Social conditions -- History South Africa -- Economic conditions Malaysia -- Economic conditions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2780 , http://hdl.handle.net/10962/d1002990
- Description: The focus of this thesis is on the bilateral relationship between South Africa and Malaysia. The thesis appropriates ‘critical theory,’ and as a flexible theoretical tool, and, as an open-ended, loose frame in order to give voice to the marginalized and voiceless from the South. The thesis thus looks at the politico-economic ties that have been developed and brings into view the socio-cultural relations that had been established between the peoples of the two sovereign nation-states during the apartheid and post-apartheid eras respectively. The basic purpose of this study was fivefold: (a) to contribute to the extant literature that concentrates on South Africa’s relations with Malaysia, (b) to examine the relationship at political and economic ties in some detail, (c) to demonstrate that apart from the afore-mentioned bonds IR specialists should also take into account the socio-cultural dimensions of international relations, (d) to bring to light the nation-state’s limitations when discussing the role of non-state actors and considering the contributions of other factors such as globalization, and (e) to stimulate further research on bilateral and multilateral relations in the South – particularly between South Africa and other states in Asia and Latin America - that would assist to better understand the past, present and perhaps the future.
- Full Text:
- Date Issued: 2008
- Authors: Haron, Muhammed
- Date: 2008
- Subjects: Critical theory South Africa -- Foreign relations -- Malaysia Malaysia -- Foreign relations -- South Africa South Africa -- Politics and government -- History Malaysia -- Politics and government -- History South Africa -- Politics and government Malaysia -- Politics and government South Africa -- Social conditions -- History Malaysia -- Social conditions -- History South Africa -- Economic conditions Malaysia -- Economic conditions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2780 , http://hdl.handle.net/10962/d1002990
- Description: The focus of this thesis is on the bilateral relationship between South Africa and Malaysia. The thesis appropriates ‘critical theory,’ and as a flexible theoretical tool, and, as an open-ended, loose frame in order to give voice to the marginalized and voiceless from the South. The thesis thus looks at the politico-economic ties that have been developed and brings into view the socio-cultural relations that had been established between the peoples of the two sovereign nation-states during the apartheid and post-apartheid eras respectively. The basic purpose of this study was fivefold: (a) to contribute to the extant literature that concentrates on South Africa’s relations with Malaysia, (b) to examine the relationship at political and economic ties in some detail, (c) to demonstrate that apart from the afore-mentioned bonds IR specialists should also take into account the socio-cultural dimensions of international relations, (d) to bring to light the nation-state’s limitations when discussing the role of non-state actors and considering the contributions of other factors such as globalization, and (e) to stimulate further research on bilateral and multilateral relations in the South – particularly between South Africa and other states in Asia and Latin America - that would assist to better understand the past, present and perhaps the future.
- Full Text:
- Date Issued: 2008
South African public private partnership (PPP) projects
- Nyagwachi, Josiah Nyangaresi
- Authors: Nyagwachi, Josiah Nyangaresi
- Date: 2008
- Subjects: Public-private sector cooperation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:9696 , http://hdl.handle.net/10948/716 , Public-private sector cooperation -- South Africa
- Description: The purpose of this thesis is to disseminate research work done towards a higher degree and report on the findings of the research that was conducted relative to South African Public Private Partnership (PPP) projects. The research investigated perceptions of PPP actors on the performance of operational PPP projects. The aim of the research was to fulfil the requirements for the award of the degree of philosophiae doctor in construction management; contribute to the PPP body of knowledge; contribute further understanding of the performance of PPP projects in South Africa; and develop a systemic model for a sustainable PPP system within the country and beyond. All the aforementioned have been achieved, despite the research limitations as indicated in Chapter 1. A case study approach was adopted to examine various performance aspects of operational South African PPP projects. The research was a multi-case study design. Each individual case study consisted of a ‘whole’ study, in which facts were gathered from the selected PPP projects and conclusions drawn on those facts. A web-based questionnaire was used to capture the experiences and perceptions of various actors involved directly, or indirectly in selected PPP projects. The sample stratum consisted of all operational PPP projects registered in accordance with Treasury Regulations as of December 2005 and other projects that reached financial closure before the Public Finance Management Act of 1999 became effective. PPPs involve highly complex procurement processes, are relatively new in South Africa and to date have attracted limited investigation to refine our understanding of the operational performance of PPP projects. This is notable, as significant financial and other resources are involved, and the perception exists that service delivery in most parts of the country is poor. Key empirical evidence from the research indicates that South Africa has developed a robust policy and regulatory framework for PPPs; has an inadequate level of PPP awareness and training; and lacks the project management capacity to facilitate deal flow. It is suggested that further research be conducted on a yearly basis, preferably every six months, so that trends can be established concerning various aspects of other operational PPPs. Further, it is recommended that the PPP Unit commission sector-specific studies that will conduct further research, to compare research across PPP and non-PPP contracts. The choice to conduct a multi-case study required extensive resources and time beyond the means available to the researcher. Further, the sensitive nature of PPP projects made it difficult to obtain required data at the first attempt. However, the researcher made several follow up calls and reminders before eventually obtaining the required data from the respondents. A systemic PPP model has been developed for PPP implementation and management. This model was tested for appropriateness by conducting a further survey on PPP participants attending an international conference on 'Financing of Infrastructure Development in Africa through Public Private Partnerships’ staged in August 2007, in the St. George Hotel, Johannesburg, South Africa. The findings from this research make an invaluable and original contribution to the PPP body of knowledge, provide insight for further research in this important field, refine the understanding of operational PPP projects, and provide direction for policy and decision makers in the public and private sectors, within South Africa and beyond.
- Full Text:
- Date Issued: 2008
- Authors: Nyagwachi, Josiah Nyangaresi
- Date: 2008
- Subjects: Public-private sector cooperation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:9696 , http://hdl.handle.net/10948/716 , Public-private sector cooperation -- South Africa
- Description: The purpose of this thesis is to disseminate research work done towards a higher degree and report on the findings of the research that was conducted relative to South African Public Private Partnership (PPP) projects. The research investigated perceptions of PPP actors on the performance of operational PPP projects. The aim of the research was to fulfil the requirements for the award of the degree of philosophiae doctor in construction management; contribute to the PPP body of knowledge; contribute further understanding of the performance of PPP projects in South Africa; and develop a systemic model for a sustainable PPP system within the country and beyond. All the aforementioned have been achieved, despite the research limitations as indicated in Chapter 1. A case study approach was adopted to examine various performance aspects of operational South African PPP projects. The research was a multi-case study design. Each individual case study consisted of a ‘whole’ study, in which facts were gathered from the selected PPP projects and conclusions drawn on those facts. A web-based questionnaire was used to capture the experiences and perceptions of various actors involved directly, or indirectly in selected PPP projects. The sample stratum consisted of all operational PPP projects registered in accordance with Treasury Regulations as of December 2005 and other projects that reached financial closure before the Public Finance Management Act of 1999 became effective. PPPs involve highly complex procurement processes, are relatively new in South Africa and to date have attracted limited investigation to refine our understanding of the operational performance of PPP projects. This is notable, as significant financial and other resources are involved, and the perception exists that service delivery in most parts of the country is poor. Key empirical evidence from the research indicates that South Africa has developed a robust policy and regulatory framework for PPPs; has an inadequate level of PPP awareness and training; and lacks the project management capacity to facilitate deal flow. It is suggested that further research be conducted on a yearly basis, preferably every six months, so that trends can be established concerning various aspects of other operational PPPs. Further, it is recommended that the PPP Unit commission sector-specific studies that will conduct further research, to compare research across PPP and non-PPP contracts. The choice to conduct a multi-case study required extensive resources and time beyond the means available to the researcher. Further, the sensitive nature of PPP projects made it difficult to obtain required data at the first attempt. However, the researcher made several follow up calls and reminders before eventually obtaining the required data from the respondents. A systemic PPP model has been developed for PPP implementation and management. This model was tested for appropriateness by conducting a further survey on PPP participants attending an international conference on 'Financing of Infrastructure Development in Africa through Public Private Partnerships’ staged in August 2007, in the St. George Hotel, Johannesburg, South Africa. The findings from this research make an invaluable and original contribution to the PPP body of knowledge, provide insight for further research in this important field, refine the understanding of operational PPP projects, and provide direction for policy and decision makers in the public and private sectors, within South Africa and beyond.
- Full Text:
- Date Issued: 2008
Strategies to improve business success in selected industries
- Authors: Dayan, Oren
- Date: 2008
- Subjects: Success in business , Business -- Management , Customer relations -- Management
- Language: English
- Type: Thesis , Doctoral , DCom
- Identifier: vital:9366 , http://hdl.handle.net/10948/938 , Success in business , Business -- Management , Customer relations -- Management
- Description: Successful economies are dependent on successful industries.The present study explores how business success could be improved in three selected industries, namely the motorcar, high-technology and food manufacturing industries. These industries are vital to growing the economy of countries. The present study made a significant contribution towords identifying a theoretical model to improve the business success of the motorcar, high technology amd the food manufacturing industries. The study showed that various combinations of product launching stategies (distribution channel development, product image, third-party agreements, pricing, e-business, and e-saving), as well as organisational variables (TQM and market culture) are important agreements to achieve increased sales growth and CRM effectiveness.
- Full Text:
- Date Issued: 2008
- Authors: Dayan, Oren
- Date: 2008
- Subjects: Success in business , Business -- Management , Customer relations -- Management
- Language: English
- Type: Thesis , Doctoral , DCom
- Identifier: vital:9366 , http://hdl.handle.net/10948/938 , Success in business , Business -- Management , Customer relations -- Management
- Description: Successful economies are dependent on successful industries.The present study explores how business success could be improved in three selected industries, namely the motorcar, high-technology and food manufacturing industries. These industries are vital to growing the economy of countries. The present study made a significant contribution towords identifying a theoretical model to improve the business success of the motorcar, high technology amd the food manufacturing industries. The study showed that various combinations of product launching stategies (distribution channel development, product image, third-party agreements, pricing, e-business, and e-saving), as well as organisational variables (TQM and market culture) are important agreements to achieve increased sales growth and CRM effectiveness.
- 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
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
Studies on the use of essential oils for the control of Sitophilus Zeamais (Motschulsky) (Coleoptera; Curculionidae): a pest of stored maize grains
- Odeyemi, Oluwakemi Oluwaseyi
- Authors: Odeyemi, Oluwakemi Oluwaseyi
- Date: 2008
- Subjects: Curculionidae , Essences and essential oils , Corn -- Diseases and pests -- South Africa , Biological pest control agents -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD (Botany)
- Identifier: vital:11301 , http://hdl.handle.net/10353/168 , Curculionidae , Essences and essential oils , Corn -- Diseases and pests -- South Africa , Biological pest control agents -- South Africa
- Description: The common maize weevil, Sitophilus zeamais Motschulsky (Coleoptera: Curculionidae), a well known pest of stored-maize grain in most parts of the world, was identified as one of the major constraints of harvested maize grains in the Eastern Cape Province, South Africa. The use of plants or their products is one of the recent methods being investigated for insect pest control worldwide. Therefore, the main aim of the present study was to identify available plants in the Eastern Cape that could be used to combat the problem of Sitophilus zeamais in stored-maize grains. For the realization of the aims of this research, the following studies were carried out; a preliminary survey was conducted to obtain baseline information on the farmers’ knowledge and experience of indigenous insect pest control methods in the Eastern Cape. Also, studies on the insecticidal potential of the essential oils of some plants were investigated against the maize weevil. The quality parameters of maize grains treated with the essential oils was also studied and, using a rat model, the toxicity of the essential oils was investigated. The outcome from this study revealed that there is awareness amongst the farmers in the Eastern Cape on the use of plants or their products to control insect pests. Unfortunately, such methods are currently being neglected and the knowledge of their application was found to be eroding. Among the various essential oils screened were those from Mentha longifolia L. and Tagetes minuta L. which evoked an appreciable level of contact, fumigant and repellent toxicity on the maize weevil. Further work done to determine the effects of the oils on maize stored over a period of three months revealed that the two oils had no adverse effect on the proximate compositions and some quality parameters of the stored maize. However, the toxicological study conducted on rats showed that the oils at tested concentrations exhibited some level of toxicity. It is, therefore, suggested that the essential oils of M. longifolia and T. minuta should not be used to treat maize grains intended for human consumption.
- Full Text:
- Date Issued: 2008
- Authors: Odeyemi, Oluwakemi Oluwaseyi
- Date: 2008
- Subjects: Curculionidae , Essences and essential oils , Corn -- Diseases and pests -- South Africa , Biological pest control agents -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD (Botany)
- Identifier: vital:11301 , http://hdl.handle.net/10353/168 , Curculionidae , Essences and essential oils , Corn -- Diseases and pests -- South Africa , Biological pest control agents -- South Africa
- Description: The common maize weevil, Sitophilus zeamais Motschulsky (Coleoptera: Curculionidae), a well known pest of stored-maize grain in most parts of the world, was identified as one of the major constraints of harvested maize grains in the Eastern Cape Province, South Africa. The use of plants or their products is one of the recent methods being investigated for insect pest control worldwide. Therefore, the main aim of the present study was to identify available plants in the Eastern Cape that could be used to combat the problem of Sitophilus zeamais in stored-maize grains. For the realization of the aims of this research, the following studies were carried out; a preliminary survey was conducted to obtain baseline information on the farmers’ knowledge and experience of indigenous insect pest control methods in the Eastern Cape. Also, studies on the insecticidal potential of the essential oils of some plants were investigated against the maize weevil. The quality parameters of maize grains treated with the essential oils was also studied and, using a rat model, the toxicity of the essential oils was investigated. The outcome from this study revealed that there is awareness amongst the farmers in the Eastern Cape on the use of plants or their products to control insect pests. Unfortunately, such methods are currently being neglected and the knowledge of their application was found to be eroding. Among the various essential oils screened were those from Mentha longifolia L. and Tagetes minuta L. which evoked an appreciable level of contact, fumigant and repellent toxicity on the maize weevil. Further work done to determine the effects of the oils on maize stored over a period of three months revealed that the two oils had no adverse effect on the proximate compositions and some quality parameters of the stored maize. However, the toxicological study conducted on rats showed that the oils at tested concentrations exhibited some level of toxicity. It is, therefore, suggested that the essential oils of M. longifolia and T. minuta should not be used to treat maize grains intended for human consumption.
- 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
The ecology and conservation of Mackinder's eagle owls (Bubo capensis mackinderi) in central Kenya in relation to agricultural land-use and cultural attitudes
- Authors: Ogada, Darcy L
- Date: 2008
- Subjects: Cape eagle owl -- Kenya Cape eagle owl -- Habitat -- Kenya Cape eagle owl -- Breeding -- Kenya Cape eagle owl -- Nutrition -- Kenya Bubo -- Kenya Wildlife conservation -- Kenya Biodiversity conservation -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5668 , http://hdl.handle.net/10962/d1005353
- Description: The loss of habitat to agriculture is a worldwide problem for biodiversity conservation. One species that has seemingly been able to adapt to the conversion of forests to farmlands is Mackinder’s eagle owl (Bubo capensis mackinderi), which inhabits highland areas, but little is known of its ecology, especially outside of protected areas. This study examined the impact of agricultural practices and farmer’s attitudes on the foraging and population ecology of the Mackinder’s eagle owl in central Kenya. Owl territories were monitored monthly from June 2004- October 2006 for signs of occupancy, breeding activity, mortality and to collect data on food resources. Nest site characteristics were measured for all known nests. Because previous studies showed an affinity for rodents, small mammals were trapped monthly using mark-recapture methodology. In each territory, the type and amount of farm crops were measured each month and farmers were interviewed about their knowledge and beliefs about owls. Mackinder’s eagle owls in central Kenya lived at extremely high density 0.87 owl pairs/km². This density was high compared to other populations of Mackinder’s eagle owl and to Eurasian eagle owl (Bubo bubo) populations in Europe. Breeding success was 48% over three years and this compared well with other species of eagle owl inhabiting human-disturbed areas. All nests and roosts were located in river valleys, and all successful nest sites were located on cliffs or other inaccessible rocky terrain. Nest sites were located adjacent to farms, which provided for both open hunting and an abundance of prey. Breeding activity was concentrated after the rainy seasons and this was likely linked to prey availability after the rains. Agricultural activities generally had a positive effect on rodent populations. Small mammal trapping results revealed that rodents were over 14 times more abundant in farms than in adjacent grassland habitat. This population of Mackinder’s eagle owl had a very catholic diet and consumed mostly mammalian prey species including hares, giant rats, root rats, grooved-tooth rats and small rodents. Small rodents accounted for almost half of the owls’ diet and when their numbers increased, owls responded by consuming more of them, indicating the importance of farming activities to this population of owls. Other populations of eagle owl inhabiting human-disturbed areas had diet widths positively related to levels of habitat disturbance. This result supported optimal foraging theory that more productive environments have predators with more specialized diets, while patchy environments have generalist predators. The ecology of this population of Mackinder’s eagle owls was heavily influenced by human agricultural activities, which generally had a positive effect on their population. Farming activities changed rapidly both within and between seasons as plots were small and neighbouring farmers planted various crops at different times of the year and this was enhanced by irrigation in some areas. Year-round availability of forage within farms had a positive effect on owl prey species, some of which increased relative to the type and amount of crops found in farms. However, 57% of owl injuries and mortalities that occurred were related either directly or indirectly to human activities. Cultural prejudices against owls remain the biggest threat to this population’s long-term persistence. Farmer education was shown to play a significant role in overcoming negative beliefs about owls. Because Mackinder’s eagle owls are highly adaptable to anthropomorphic landscape changes, largely due to their adaptability as food generalists, they are one of the few top predators remaining in this highly disturbed agricultural system. However, populations within agricultural areas remain especially vulnerable to negative human attitudes towards owls due to their close association with human activities.
- Full Text:
- Date Issued: 2008
- Authors: Ogada, Darcy L
- Date: 2008
- Subjects: Cape eagle owl -- Kenya Cape eagle owl -- Habitat -- Kenya Cape eagle owl -- Breeding -- Kenya Cape eagle owl -- Nutrition -- Kenya Bubo -- Kenya Wildlife conservation -- Kenya Biodiversity conservation -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5668 , http://hdl.handle.net/10962/d1005353
- Description: The loss of habitat to agriculture is a worldwide problem for biodiversity conservation. One species that has seemingly been able to adapt to the conversion of forests to farmlands is Mackinder’s eagle owl (Bubo capensis mackinderi), which inhabits highland areas, but little is known of its ecology, especially outside of protected areas. This study examined the impact of agricultural practices and farmer’s attitudes on the foraging and population ecology of the Mackinder’s eagle owl in central Kenya. Owl territories were monitored monthly from June 2004- October 2006 for signs of occupancy, breeding activity, mortality and to collect data on food resources. Nest site characteristics were measured for all known nests. Because previous studies showed an affinity for rodents, small mammals were trapped monthly using mark-recapture methodology. In each territory, the type and amount of farm crops were measured each month and farmers were interviewed about their knowledge and beliefs about owls. Mackinder’s eagle owls in central Kenya lived at extremely high density 0.87 owl pairs/km². This density was high compared to other populations of Mackinder’s eagle owl and to Eurasian eagle owl (Bubo bubo) populations in Europe. Breeding success was 48% over three years and this compared well with other species of eagle owl inhabiting human-disturbed areas. All nests and roosts were located in river valleys, and all successful nest sites were located on cliffs or other inaccessible rocky terrain. Nest sites were located adjacent to farms, which provided for both open hunting and an abundance of prey. Breeding activity was concentrated after the rainy seasons and this was likely linked to prey availability after the rains. Agricultural activities generally had a positive effect on rodent populations. Small mammal trapping results revealed that rodents were over 14 times more abundant in farms than in adjacent grassland habitat. This population of Mackinder’s eagle owl had a very catholic diet and consumed mostly mammalian prey species including hares, giant rats, root rats, grooved-tooth rats and small rodents. Small rodents accounted for almost half of the owls’ diet and when their numbers increased, owls responded by consuming more of them, indicating the importance of farming activities to this population of owls. Other populations of eagle owl inhabiting human-disturbed areas had diet widths positively related to levels of habitat disturbance. This result supported optimal foraging theory that more productive environments have predators with more specialized diets, while patchy environments have generalist predators. The ecology of this population of Mackinder’s eagle owls was heavily influenced by human agricultural activities, which generally had a positive effect on their population. Farming activities changed rapidly both within and between seasons as plots were small and neighbouring farmers planted various crops at different times of the year and this was enhanced by irrigation in some areas. Year-round availability of forage within farms had a positive effect on owl prey species, some of which increased relative to the type and amount of crops found in farms. However, 57% of owl injuries and mortalities that occurred were related either directly or indirectly to human activities. Cultural prejudices against owls remain the biggest threat to this population’s long-term persistence. Farmer education was shown to play a significant role in overcoming negative beliefs about owls. Because Mackinder’s eagle owls are highly adaptable to anthropomorphic landscape changes, largely due to their adaptability as food generalists, they are one of the few top predators remaining in this highly disturbed agricultural system. However, populations within agricultural areas remain especially vulnerable to negative human attitudes towards owls due to their close association with human activities.
- Full Text:
- Date Issued: 2008
The effects of elephants at low densities and after short occupation time on the ecosystems of the Eastern Cape Province, South Africa
- Authors: Parker, Daniel Matthew
- Date: 2008
- Subjects: Elephants -- South Africa -- Eastern Cape Biotic communities -- South Africa -- Eastern Cape Animal populations -- South Africa -- Eastern Cape Plant communities -- South Africa -- Eastern Cape Mammals -- Ecology -- South Africa -- Eastern Cape Animal-plant relationships -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5678 , http://hdl.handle.net/10962/d1005363
- Description: Elephants (Loxodonta africana, Blumenbach) are recognised as keystone herbivores and ecosystem engineers in African ecosystems due to the noticeable impact they have on plant communities. This impact can influence other animal taxa and ecosystem processes, especially within enclosed systems. I investigated the effects of elephants in four vegetation types and the cascade effect on three associated taxa and two ecosystem processes at five sites with elephants and five paired sites without elephants in the Eastern Cape Province, South Africa, between April 2005 and July 2007. In grassland habitats, the physical structure of the vegetation was neither enhanced nor degraded in the presence of elephants. Within the locally important Thicket Biome, elephant browsing transformed relatively homogeneous stands of vegetation into more heterogeneous units. However, although seeds from thicket plant species were recorded in elephant dung, elephants did not promote the viability and germination success of these plants. In addition, elephant foraging on aloes caused declines in their populations. By contrast, the size of bushclumps was not reduced in the presence of elephants in bushclump savanna. The associated insect, bird and mammal communities appeared to benefit from elephant foraging in all vegetation types assessed, whereas vegetation patch dynamics and soil surface processes were neither enhanced nor degraded in the presence of elephants. I conclude that, at current densities, elephants do not (in most cases) negatively affect plant and animal communities or ecosystem processes in enclosed reserves. However, elephants have only been present at each site for a relatively short period and it is likely that their impact will be cumulative, increasing over time in these closed systems. Thus, future research along a continuum of elephant density and time since re-introduction is recommended.
- Full Text:
- Date Issued: 2008
- Authors: Parker, Daniel Matthew
- Date: 2008
- Subjects: Elephants -- South Africa -- Eastern Cape Biotic communities -- South Africa -- Eastern Cape Animal populations -- South Africa -- Eastern Cape Plant communities -- South Africa -- Eastern Cape Mammals -- Ecology -- South Africa -- Eastern Cape Animal-plant relationships -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5678 , http://hdl.handle.net/10962/d1005363
- Description: Elephants (Loxodonta africana, Blumenbach) are recognised as keystone herbivores and ecosystem engineers in African ecosystems due to the noticeable impact they have on plant communities. This impact can influence other animal taxa and ecosystem processes, especially within enclosed systems. I investigated the effects of elephants in four vegetation types and the cascade effect on three associated taxa and two ecosystem processes at five sites with elephants and five paired sites without elephants in the Eastern Cape Province, South Africa, between April 2005 and July 2007. In grassland habitats, the physical structure of the vegetation was neither enhanced nor degraded in the presence of elephants. Within the locally important Thicket Biome, elephant browsing transformed relatively homogeneous stands of vegetation into more heterogeneous units. However, although seeds from thicket plant species were recorded in elephant dung, elephants did not promote the viability and germination success of these plants. In addition, elephant foraging on aloes caused declines in their populations. By contrast, the size of bushclumps was not reduced in the presence of elephants in bushclump savanna. The associated insect, bird and mammal communities appeared to benefit from elephant foraging in all vegetation types assessed, whereas vegetation patch dynamics and soil surface processes were neither enhanced nor degraded in the presence of elephants. I conclude that, at current densities, elephants do not (in most cases) negatively affect plant and animal communities or ecosystem processes in enclosed reserves. However, elephants have only been present at each site for a relatively short period and it is likely that their impact will be cumulative, increasing over time in these closed systems. Thus, future research along a continuum of elephant density and time since re-introduction is recommended.
- Full Text:
- Date Issued: 2008
The feeding and spatial ecologies of the large carnivore guild on Kwandwe Private Game Reserve
- Authors: Bissett, Charlene
- Date: 2008
- Subjects: Wildlife conservation -- South Africa -- Eastern Cape Kwandwe Private Game Reserve Lion -- Behavior -- South Africa -- Eastern Cape Lion -- Nutrition -- South Africa -- Eastern Cape Cheetah -- Behavior -- South Africa -- Eastern Cape Cheetah -- Nutrition -- South Africa -- Eastern Cape African wild dog -- South Africa -- Eastern Cape Spatial behavior in animals Predation (Biology) Game reserves -- Management
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5802 , http://hdl.handle.net/10962/d1006195
- Description: The reintroduction of lions, cheetahs and African wild dogs to Kwandwe Private Game Reserve in the Eastern Cape Province of South Africa created the opportunity to study the biology and behaviour of these large carnivores in an enclosed system. The research focused on space utilisation and feeding ecology of the predators, using standard observational methods. Changes in the structure of the carnivore guild, and changes in the prey base that occurred during the study were used as natural experiments to examine factors affecting space use and diet. In general, the diets of the predators were similar to previous studies and prey abundance was more important than prey species size in determining prey selection. Changes in the abundance of certain prey species was matched by a dietary switch in lions from kudu to warthog and an increase in the proportion of springbok kills by the cheetahs. There was no significant difference in the proportions of prey species detected by ad hoc or continuous observations. Core areas occupied by the predators were significantly smaller than home ranges except when females were denning. Home ranges overlapped both within and between species, but there was very little overlap of core areas. An increase in the number of lion prides in the area during the study resulted in an increase in overlap of home ranges of lions and cheetahs, but did not result in a change in home range size. Space use by female cheetahs with cubs increased as the cubs grew older. The use of thicket vegetation by cheetahs decreased with an increase in the number of lion prides. Minimum Daily Energy Expenditure, energy intake and net benefit were calculated for the predators using data from continuous observations. All predators exhibited a large net benefit and the net benefit for single female cheetahs was greater than for the members of the coalition. Net benefit for the alpha pair of African wild dogs was lower than that of the pack.
- Full Text:
- Date Issued: 2008
- Authors: Bissett, Charlene
- Date: 2008
- Subjects: Wildlife conservation -- South Africa -- Eastern Cape Kwandwe Private Game Reserve Lion -- Behavior -- South Africa -- Eastern Cape Lion -- Nutrition -- South Africa -- Eastern Cape Cheetah -- Behavior -- South Africa -- Eastern Cape Cheetah -- Nutrition -- South Africa -- Eastern Cape African wild dog -- South Africa -- Eastern Cape Spatial behavior in animals Predation (Biology) Game reserves -- Management
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5802 , http://hdl.handle.net/10962/d1006195
- Description: The reintroduction of lions, cheetahs and African wild dogs to Kwandwe Private Game Reserve in the Eastern Cape Province of South Africa created the opportunity to study the biology and behaviour of these large carnivores in an enclosed system. The research focused on space utilisation and feeding ecology of the predators, using standard observational methods. Changes in the structure of the carnivore guild, and changes in the prey base that occurred during the study were used as natural experiments to examine factors affecting space use and diet. In general, the diets of the predators were similar to previous studies and prey abundance was more important than prey species size in determining prey selection. Changes in the abundance of certain prey species was matched by a dietary switch in lions from kudu to warthog and an increase in the proportion of springbok kills by the cheetahs. There was no significant difference in the proportions of prey species detected by ad hoc or continuous observations. Core areas occupied by the predators were significantly smaller than home ranges except when females were denning. Home ranges overlapped both within and between species, but there was very little overlap of core areas. An increase in the number of lion prides in the area during the study resulted in an increase in overlap of home ranges of lions and cheetahs, but did not result in a change in home range size. Space use by female cheetahs with cubs increased as the cubs grew older. The use of thicket vegetation by cheetahs decreased with an increase in the number of lion prides. Minimum Daily Energy Expenditure, energy intake and net benefit were calculated for the predators using data from continuous observations. All predators exhibited a large net benefit and the net benefit for single female cheetahs was greater than for the members of the coalition. Net benefit for the alpha pair of African wild dogs was lower than that of the pack.
- Full Text:
- Date Issued: 2008
The identification of criteria to be utilised in mathematical diagnostic tests
- Authors: Wagner-Welsh, Shirley Joy
- Date: 2008
- Subjects: Educational tests and measurements -- South Africa -- Port Elizabeth , Mathematical ability -- Testing , Ability -- Testing , Guidance test battery for secondary pupils , Mathematics -- Study and teaching -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10501 , http://hdl.handle.net/10948/708 , Educational tests and measurements -- South Africa -- Port Elizabeth , Mathematical ability -- Testing , Ability -- Testing , Guidance test battery for secondary pupils , Mathematics -- Study and teaching -- South Africa
- Description: School-related mistakes and low pass rates have led this researcher to perceive that some students are not adequately prepared for Mathematics 1. To address the problem of under-preparedness overseas universities use placement or diagnostic tests. Diagnostic testing identifies areas of weakness and provides information to guide the development of appropriate remedial support. This researcher embarked on a study to identify the sub-domains (criteria) that should be included in a diagnostic Mathematics test battery at the NMMU. An analysis of first-year curricula was undertaken to determine the required Mathematical pre-knowledge and skills entry-level students should have. Thereafter, the required pre-knowledge and skills were reflected against the standard grade school syllabi. From this it was determined that the school learners should acquire the necessary pre-knowledge and skills for university success as part of the school syllabus. However, in reality this is not the case as the researcher and other Mathematics lecturers identified a number of basic errors that incoming students make. This suggests that they have not developed all the required knowledge and skills. Furthermore, their performance in the matriculation examinations does not provide an adequate measure of the requisite Mathematical pre-knowledge and skills necessary for success at university-level Mathematics. No suitable existing diagnostic Mathematics test could be found. By utilizing both an action research as well as a test development methodology, the researcher thus proceeded to delineate the sub-domains that should be included in a diagnostic Mathematics test battery. Thereafter, test specifications were developed for two pilot tests and items were developed or sourced. The constructed response item-type was chosen for the pilot tests as it was argued that this item-type was more useful to use in a diagnostic test than a multiple-choice item format, for example. The pilot test battery, which consisted of a pilot Arithmetic and Algebra and Calculus tests, was administered to a sample of first-year students at the NMMU in 2004 and their performance in Mathematics at the end of the first year was tracked. Tests were scored holistically and analytically to provide a rich source of information. Thereafter, the test results were analysed to obtain evidence on the content validity of the pilot tests, including the item difficulty values and the item-total correlations; to determine the predictive validity of performance on the pilot tests with respect to final first-year Mathematics marks; and their reliability was determined using the Cronbach’s Alpha statistic. These findings suggest that appropriate sub-domains (criteria) were delineated and the items appropriately covered these sub-domains (i.e. the content validity of the pilot tests is acceptable). Furthermore, the predictive validity of the pilot ix tests was found to be acceptable in that significant correlations were found between the pilot tests and performance in first-year Mathematics. Finally, the pilot tests were found to be reliable. Based on the results, suggestions are made regarding how to refine the diagnostic test battery and the research related to it. The final diagnostic Mathematics test battery holds much potential to be able to assist in the early identification of at-risk students who can be timeously placed in developmentally appropriate Mathematics modules or provided with appropriate remedial intervention.
- Full Text:
- Date Issued: 2008
- Authors: Wagner-Welsh, Shirley Joy
- Date: 2008
- Subjects: Educational tests and measurements -- South Africa -- Port Elizabeth , Mathematical ability -- Testing , Ability -- Testing , Guidance test battery for secondary pupils , Mathematics -- Study and teaching -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10501 , http://hdl.handle.net/10948/708 , Educational tests and measurements -- South Africa -- Port Elizabeth , Mathematical ability -- Testing , Ability -- Testing , Guidance test battery for secondary pupils , Mathematics -- Study and teaching -- South Africa
- Description: School-related mistakes and low pass rates have led this researcher to perceive that some students are not adequately prepared for Mathematics 1. To address the problem of under-preparedness overseas universities use placement or diagnostic tests. Diagnostic testing identifies areas of weakness and provides information to guide the development of appropriate remedial support. This researcher embarked on a study to identify the sub-domains (criteria) that should be included in a diagnostic Mathematics test battery at the NMMU. An analysis of first-year curricula was undertaken to determine the required Mathematical pre-knowledge and skills entry-level students should have. Thereafter, the required pre-knowledge and skills were reflected against the standard grade school syllabi. From this it was determined that the school learners should acquire the necessary pre-knowledge and skills for university success as part of the school syllabus. However, in reality this is not the case as the researcher and other Mathematics lecturers identified a number of basic errors that incoming students make. This suggests that they have not developed all the required knowledge and skills. Furthermore, their performance in the matriculation examinations does not provide an adequate measure of the requisite Mathematical pre-knowledge and skills necessary for success at university-level Mathematics. No suitable existing diagnostic Mathematics test could be found. By utilizing both an action research as well as a test development methodology, the researcher thus proceeded to delineate the sub-domains that should be included in a diagnostic Mathematics test battery. Thereafter, test specifications were developed for two pilot tests and items were developed or sourced. The constructed response item-type was chosen for the pilot tests as it was argued that this item-type was more useful to use in a diagnostic test than a multiple-choice item format, for example. The pilot test battery, which consisted of a pilot Arithmetic and Algebra and Calculus tests, was administered to a sample of first-year students at the NMMU in 2004 and their performance in Mathematics at the end of the first year was tracked. Tests were scored holistically and analytically to provide a rich source of information. Thereafter, the test results were analysed to obtain evidence on the content validity of the pilot tests, including the item difficulty values and the item-total correlations; to determine the predictive validity of performance on the pilot tests with respect to final first-year Mathematics marks; and their reliability was determined using the Cronbach’s Alpha statistic. These findings suggest that appropriate sub-domains (criteria) were delineated and the items appropriately covered these sub-domains (i.e. the content validity of the pilot tests is acceptable). Furthermore, the predictive validity of the pilot ix tests was found to be acceptable in that significant correlations were found between the pilot tests and performance in first-year Mathematics. Finally, the pilot tests were found to be reliable. Based on the results, suggestions are made regarding how to refine the diagnostic test battery and the research related to it. The final diagnostic Mathematics test battery holds much potential to be able to assist in the early identification of at-risk students who can be timeously placed in developmentally appropriate Mathematics modules or provided with appropriate remedial intervention.
- Full Text:
- Date Issued: 2008
The impact of the identification process and the corporate social responsibility process on the effectiveness of multi-racial advertising in South Africa
- Authors: Johnson, Guillaume Desire
- Date: 2008
- Subjects: Marketing -- South Africa Advertising -- South Africa Sales promotion -- South Africa Consumers' preferences -- South Africa Marketing research -- South Africa Consumer behavior -- South Africa Consumption (Economics) -- Social aspect Attribution (Social psychology) South Africans -- Race identity Race awareness -- South Africa Ethnopsychology -- South Africa Group identity Racially mixed people
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1196 , http://hdl.handle.net/10962/d1008263
- Description: Selecting actors to appear in an advertisement is an important decision which has a crucial impact on the effectiveness of an advertising campaign. The same message, delivered by different actors, produces varying outcomes among consumers. This dilemma concerning the choice of actors occurs particularly in multi-racial societies, such as South Africa, where advertisers have to target different sectors of the community. In multi-racial societies, the choice of actors in advertisements goes beyond the usual commercial reasons. Indeed, two dimensions are generally conferred to multi-racial advertising. Firstly, the use of multi-racial representations allows for the targeting of a wider population that also owns a wider purchasing power. Marketers who want to market their brand use, for example, white and black actors so that white and black consumers can identify with the actors and recognize themselves as the target of the advertisement. Secondly, the multi-racial representations of this type of advertising hold a social role that counteracts the segregated depiction of the society. Consumers who are exposed to a multi-racial advertisement might perceive this social dimension and attribute a social responsibility to the advertisement. The purpose of this thesis is to examine the influence of the above dimensions on the effectiveness of a multi-racial advertisement. On the one hand, this study investigates the Identification Process followed by a consumer exposed to a multi-racial advertisement. On the other hand, it examines how consumers attribute a social responsibility to a specific multiracial advertisement and how this attribution, in turn, influences their responses to the advertisement and brand. Finally, the impacts of both of these dimensions on consumer behaviour are compared and the most persuasive dimension is identified. This thesis draws on Attribution Theory and Identification Theory in arguing that there are strong economic imperatives for adopting a multi-racial advertising approach. The thesis develops a conceptual framework and tests empirically hypotheses regarding the key constructs and moderating variables. The empirical results point out that both dimensions symbiotically influence the effectiveness of a multi-racial advertisement. Specifically, the results highlight that the social responsibility attributed by the viewers to the advertisement influences their behaviour more than the Identification Process.
- Full Text:
- Date Issued: 2008
- Authors: Johnson, Guillaume Desire
- Date: 2008
- Subjects: Marketing -- South Africa Advertising -- South Africa Sales promotion -- South Africa Consumers' preferences -- South Africa Marketing research -- South Africa Consumer behavior -- South Africa Consumption (Economics) -- Social aspect Attribution (Social psychology) South Africans -- Race identity Race awareness -- South Africa Ethnopsychology -- South Africa Group identity Racially mixed people
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1196 , http://hdl.handle.net/10962/d1008263
- Description: Selecting actors to appear in an advertisement is an important decision which has a crucial impact on the effectiveness of an advertising campaign. The same message, delivered by different actors, produces varying outcomes among consumers. This dilemma concerning the choice of actors occurs particularly in multi-racial societies, such as South Africa, where advertisers have to target different sectors of the community. In multi-racial societies, the choice of actors in advertisements goes beyond the usual commercial reasons. Indeed, two dimensions are generally conferred to multi-racial advertising. Firstly, the use of multi-racial representations allows for the targeting of a wider population that also owns a wider purchasing power. Marketers who want to market their brand use, for example, white and black actors so that white and black consumers can identify with the actors and recognize themselves as the target of the advertisement. Secondly, the multi-racial representations of this type of advertising hold a social role that counteracts the segregated depiction of the society. Consumers who are exposed to a multi-racial advertisement might perceive this social dimension and attribute a social responsibility to the advertisement. The purpose of this thesis is to examine the influence of the above dimensions on the effectiveness of a multi-racial advertisement. On the one hand, this study investigates the Identification Process followed by a consumer exposed to a multi-racial advertisement. On the other hand, it examines how consumers attribute a social responsibility to a specific multiracial advertisement and how this attribution, in turn, influences their responses to the advertisement and brand. Finally, the impacts of both of these dimensions on consumer behaviour are compared and the most persuasive dimension is identified. This thesis draws on Attribution Theory and Identification Theory in arguing that there are strong economic imperatives for adopting a multi-racial advertising approach. The thesis develops a conceptual framework and tests empirically hypotheses regarding the key constructs and moderating variables. The empirical results point out that both dimensions symbiotically influence the effectiveness of a multi-racial advertisement. Specifically, the results highlight that the social responsibility attributed by the viewers to the advertisement influences their behaviour more than the Identification Process.
- Full Text:
- Date Issued: 2008
The rhizosphere as a bioprocess environment for the bioconversion of hard coal
- Authors: Igbinigie, Eric Egbe
- Date: 2008
- Subjects: Rhizosphere Biotechnology Bermuda grass Coal -- Microbiology Biomass conversion
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3924 , http://hdl.handle.net/10962/d1003983
- Description: Fundamental processes involved in the microbial degradation of coal and its derivatives have been well investigated and documented over the past two decades. However, limited progress in industrial application has been identified as bottleneck in further active development of the field. The sporadic and unanticipated growth of Cynodon dactylon (Bermuda grass) has been observed on the surface of some coal dumps in the Witbank coal mining area of South Africa. Preliminary investigations showed the formation of a humic soil-like material from the breakdown of hard coal in the root zone of these plants. The potential of this system to contribute to industrial scale bioprocessing of hard coal was investigated. This study involved an investigation of the C. dactylon/coal rhizosphere environment and demonstrated the presence of fungal species with known coal bioconversion capability. Amongst these Neosartorya fischeri was identified and its activity in coal bioconversion was described for the first time. Cynodon dactylon plant roots were also shown to be colonized by mycorrhizal fungi including Glomus, Paraglomus and Gigaspora species. The role of plant photosynthate translocation into the root zone, providing organic carbon supplementation of fungal coal bioconversion was investigated in deep liquid culture with the N. fischeri isolate used as the biocatalyst. Organic acids, sugars and complex organic carbon sources were investigated and it was shown that glutamate provided significant enhancement of bioconversion activity in this system. The performance of N. fischeri in coal bioconversion was compared with Phanaerochaete chrysosporium and Trametes versicolor, both previously described fungal species in the coal bioconversion application. Fourier transform infrared spectroscopy indicated more pronounced oxidation and introduction of nitro groups in the matrix of the humic acid product of coal bioconversion in N. fischeri and P. chrysosporium than for T. versicolor. Macro-elemental analysis of biomass-bound humic acid obtained from the N. fischeri catalyzed reaction showed an increase in the oxygen and nitrogen components and coupled with a reduction in carbon and hydrogen. Pyrolysis gas chromatography mass spectroscopy further supported the proposal that the mechanism of bioconversion involves oxygen and nitrogen insertion into the coal structure. The C. dactylon bituminous hard coal dump environment was simulated in a fixed-bed perfusion column bioreactor in which the contribution of organic supplement by the plant/mycorrhizal component of the system was investigated. The results enabled the proposal of a descriptive model accounting for the performance of the system in which the plant/mycorrhizal component introduces organic substances into the root zone. The non-mycorrhizal fungi utilize the organic carbon supplement in its attack on the coal substrate, breaking it down, and releasing plant nutrients and a soil-like substrate which in turn enables the growth of C. dactylon in this hostile environment. Based on these results, the Stacked Heap Coal Bioreactor concept was developed as a large-scale industrial bioprocess application based on heap-leach mineral processing technology. Field studies have confirmed that bituminous hard coal can be converted to a humic acid rich substrate in a stacked heap system inoculated with mycorrhizal and N. fischeri cultures and planted with C. dactylon.
- Full Text:
- Date Issued: 2008
- Authors: Igbinigie, Eric Egbe
- Date: 2008
- Subjects: Rhizosphere Biotechnology Bermuda grass Coal -- Microbiology Biomass conversion
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3924 , http://hdl.handle.net/10962/d1003983
- Description: Fundamental processes involved in the microbial degradation of coal and its derivatives have been well investigated and documented over the past two decades. However, limited progress in industrial application has been identified as bottleneck in further active development of the field. The sporadic and unanticipated growth of Cynodon dactylon (Bermuda grass) has been observed on the surface of some coal dumps in the Witbank coal mining area of South Africa. Preliminary investigations showed the formation of a humic soil-like material from the breakdown of hard coal in the root zone of these plants. The potential of this system to contribute to industrial scale bioprocessing of hard coal was investigated. This study involved an investigation of the C. dactylon/coal rhizosphere environment and demonstrated the presence of fungal species with known coal bioconversion capability. Amongst these Neosartorya fischeri was identified and its activity in coal bioconversion was described for the first time. Cynodon dactylon plant roots were also shown to be colonized by mycorrhizal fungi including Glomus, Paraglomus and Gigaspora species. The role of plant photosynthate translocation into the root zone, providing organic carbon supplementation of fungal coal bioconversion was investigated in deep liquid culture with the N. fischeri isolate used as the biocatalyst. Organic acids, sugars and complex organic carbon sources were investigated and it was shown that glutamate provided significant enhancement of bioconversion activity in this system. The performance of N. fischeri in coal bioconversion was compared with Phanaerochaete chrysosporium and Trametes versicolor, both previously described fungal species in the coal bioconversion application. Fourier transform infrared spectroscopy indicated more pronounced oxidation and introduction of nitro groups in the matrix of the humic acid product of coal bioconversion in N. fischeri and P. chrysosporium than for T. versicolor. Macro-elemental analysis of biomass-bound humic acid obtained from the N. fischeri catalyzed reaction showed an increase in the oxygen and nitrogen components and coupled with a reduction in carbon and hydrogen. Pyrolysis gas chromatography mass spectroscopy further supported the proposal that the mechanism of bioconversion involves oxygen and nitrogen insertion into the coal structure. The C. dactylon bituminous hard coal dump environment was simulated in a fixed-bed perfusion column bioreactor in which the contribution of organic supplement by the plant/mycorrhizal component of the system was investigated. The results enabled the proposal of a descriptive model accounting for the performance of the system in which the plant/mycorrhizal component introduces organic substances into the root zone. The non-mycorrhizal fungi utilize the organic carbon supplement in its attack on the coal substrate, breaking it down, and releasing plant nutrients and a soil-like substrate which in turn enables the growth of C. dactylon in this hostile environment. Based on these results, the Stacked Heap Coal Bioreactor concept was developed as a large-scale industrial bioprocess application based on heap-leach mineral processing technology. Field studies have confirmed that bituminous hard coal can be converted to a humic acid rich substrate in a stacked heap system inoculated with mycorrhizal and N. fischeri cultures and planted with C. dactylon.
- Full Text:
- Date Issued: 2008
The role of discourse in the constitution of radiographic knowledge: a critical realist account
- Authors: Wright, Jennifer Lynne
- Date: 2008
- Subjects: Education, Higher -- South Africa Universities and colleges -- South Africa English language -- Study and teaching (Higher) -- South Africa Language and education Discourse analysis Radiography -- Study and teaching
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1320 , http://hdl.handle.net/10962/d1003953
- Description: The ways in which knowledge is constituted in Higher Education in South Africa today needs to take into account the historical diversity of learners’ academic and literacy competencies. The thesis begins by considering the ways in which, historically, many learners in Higher Education have been under prepared for the challenges of studying complex disciplines through the medium of English, which is often their second or third additional language. It also considers the sometimes inappropriate response of Higher Education to the plight of these learners and the present and potential role of language specialists working in collaboration with disciplinary specialists to support these learners. In this ethnographic research, I use an ontological metatheory, critical realism, as my analytical lens. Critical realism is an appropriate analytical lens for exploring and gaining insight into the possible causal mechanisms that generate the stratified and often inscrutable nature of social reality, including the role of language and discourse in education. I employ a case study design to explore the role of discourse in lecturers and clinical radiographers’ constitution of the knowledge of entry level Radiography learners at the Groote Schuur campus of Cape Peninsula University of Technology (CPUT). Taking discourse as my unit of analysis, I develop a model of knowledge constitution based on a Hallidayan framework (1978). This model comprises two contexts of culture (Higher Education and Health Care) within which are embedded two contexts of situation (the university classroom and a clinical radiography workplace). In these contexts, I focus on how lecturers and clinical radiographers constitute radiographic knowledge through the field, tenor and mode of their discourse. My research sheds light on learners’ construal of various aspects of this process of knowledge constitution, and I consider implications for Radiography teaching and learning. I conclude that, because of the dual contexts in which the learners’ knowledge is constituted, literacy requirements in the two contexts are quite different. For this reason, learners may often be unmotivated to enhance their literacies, particularly in reading and writing; yet, in the interests of the future growth of the profession, the latter will be required of them as practitioners who conduct research and publish. I argue that the real empowerment of Radiography learners thus lies in their lecturers’ agency: there is a need for them to implement certain practices that will shape the learners’ identity, not only as clinical practitioners, but as researchers and writers. In doing this, they will ensure that the learners’ potential is realised and they have the capacity to make meaningful contributions to the growth of the future radiography profession.
- Full Text:
- Date Issued: 2008
- Authors: Wright, Jennifer Lynne
- Date: 2008
- Subjects: Education, Higher -- South Africa Universities and colleges -- South Africa English language -- Study and teaching (Higher) -- South Africa Language and education Discourse analysis Radiography -- Study and teaching
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1320 , http://hdl.handle.net/10962/d1003953
- Description: The ways in which knowledge is constituted in Higher Education in South Africa today needs to take into account the historical diversity of learners’ academic and literacy competencies. The thesis begins by considering the ways in which, historically, many learners in Higher Education have been under prepared for the challenges of studying complex disciplines through the medium of English, which is often their second or third additional language. It also considers the sometimes inappropriate response of Higher Education to the plight of these learners and the present and potential role of language specialists working in collaboration with disciplinary specialists to support these learners. In this ethnographic research, I use an ontological metatheory, critical realism, as my analytical lens. Critical realism is an appropriate analytical lens for exploring and gaining insight into the possible causal mechanisms that generate the stratified and often inscrutable nature of social reality, including the role of language and discourse in education. I employ a case study design to explore the role of discourse in lecturers and clinical radiographers’ constitution of the knowledge of entry level Radiography learners at the Groote Schuur campus of Cape Peninsula University of Technology (CPUT). Taking discourse as my unit of analysis, I develop a model of knowledge constitution based on a Hallidayan framework (1978). This model comprises two contexts of culture (Higher Education and Health Care) within which are embedded two contexts of situation (the university classroom and a clinical radiography workplace). In these contexts, I focus on how lecturers and clinical radiographers constitute radiographic knowledge through the field, tenor and mode of their discourse. My research sheds light on learners’ construal of various aspects of this process of knowledge constitution, and I consider implications for Radiography teaching and learning. I conclude that, because of the dual contexts in which the learners’ knowledge is constituted, literacy requirements in the two contexts are quite different. For this reason, learners may often be unmotivated to enhance their literacies, particularly in reading and writing; yet, in the interests of the future growth of the profession, the latter will be required of them as practitioners who conduct research and publish. I argue that the real empowerment of Radiography learners thus lies in their lecturers’ agency: there is a need for them to implement certain practices that will shape the learners’ identity, not only as clinical practitioners, but as researchers and writers. In doing this, they will ensure that the learners’ potential is realised and they have the capacity to make meaningful contributions to the growth of the future radiography profession.
- Full Text:
- Date Issued: 2008
The separation of platinum and gold from an industrial feed solution
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
The solvent-free approach versus the use of ionic liquids in the synthesis of ferrocenes
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
The zonation of coastal dune plants in relation to sand burial, resource availability and physiological adaptation
- Authors: Gilbert, Matthew Edmund
- Date: 2008
- Subjects: Sand dune conservation -- South Africa -- Eastern Cape Coastal ecology -- South Africa -- Eastern Cape Botany -- South Africa -- Eastern Cape Coastal biology -- South Africa -- Eastern Cape Littoral plants -- South Africa -- Eastern Cape Littoral plants Sand dune plants -- Ecophysiology Sand dune plants -- Geographical distribution
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4195 , http://hdl.handle.net/10962/d1003764
- Description: When considering the large amount of work done on dune ecology, and that a number of the classical ecological theories originate from work on dunes, it is apparent that there remains a need for physiological and mechanistic explanations of dune plant phenomena. This thesis demonstrated that in the extreme coastal environment dune plants must survive both high rates of burial (disturbance), and low nutrient availability (stress). The ability of four species to respond to these two factors corresponded with their position in a vegetation gradient on the dunes. A low stem tissue density was shown to enhance the potential stem elongation rate of buried plants, but reduced the maximum height to which a plant could grow. Such a tradeoff implies that tall light-competitive plants are able to survive only in stable areas, while burial responsive mobile-dune plants are limited to areas of low vegetation height. This stem tissue density tradeoff was suggested as the mechanism determining the zonation that species show within the dune vegetation gradient present at various sites in South Africa. Finally, detailed investigations of dune plant ecophysiology found that: 1) The resources used in the response to burial derive from external sources of carbon and nitrogen, as well as simple physiological and physical mechanisms of resource allocation. 2) The leaves of dune plants were found to be operating at one extreme of the photosynthetic continuum; viz efficient use of leaf nitrogen at the expense of water loss. 3) Contrary to other ecosystems, the environmental characteristics of dunes may allow plants to occupy a high disturbance, high stress niche, through the maintenance of lowered competition. 4) At least two mobile-dune species form steep dunes, and are able to optimise growth, on steeper dunes, such that they have to grow less in response to burial than plants that form more shallow dunes. In this thesis, it was shown that the link between the carbon and nitrogen economies of dune plants was pivotal in determining species distributions and survival under extreme environmental conditions. As vast areas of the world’s surface are covered by sand dunes these observations are not just of passing interest.
- Full Text:
- Date Issued: 2008
- Authors: Gilbert, Matthew Edmund
- Date: 2008
- Subjects: Sand dune conservation -- South Africa -- Eastern Cape Coastal ecology -- South Africa -- Eastern Cape Botany -- South Africa -- Eastern Cape Coastal biology -- South Africa -- Eastern Cape Littoral plants -- South Africa -- Eastern Cape Littoral plants Sand dune plants -- Ecophysiology Sand dune plants -- Geographical distribution
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4195 , http://hdl.handle.net/10962/d1003764
- Description: When considering the large amount of work done on dune ecology, and that a number of the classical ecological theories originate from work on dunes, it is apparent that there remains a need for physiological and mechanistic explanations of dune plant phenomena. This thesis demonstrated that in the extreme coastal environment dune plants must survive both high rates of burial (disturbance), and low nutrient availability (stress). The ability of four species to respond to these two factors corresponded with their position in a vegetation gradient on the dunes. A low stem tissue density was shown to enhance the potential stem elongation rate of buried plants, but reduced the maximum height to which a plant could grow. Such a tradeoff implies that tall light-competitive plants are able to survive only in stable areas, while burial responsive mobile-dune plants are limited to areas of low vegetation height. This stem tissue density tradeoff was suggested as the mechanism determining the zonation that species show within the dune vegetation gradient present at various sites in South Africa. Finally, detailed investigations of dune plant ecophysiology found that: 1) The resources used in the response to burial derive from external sources of carbon and nitrogen, as well as simple physiological and physical mechanisms of resource allocation. 2) The leaves of dune plants were found to be operating at one extreme of the photosynthetic continuum; viz efficient use of leaf nitrogen at the expense of water loss. 3) Contrary to other ecosystems, the environmental characteristics of dunes may allow plants to occupy a high disturbance, high stress niche, through the maintenance of lowered competition. 4) At least two mobile-dune species form steep dunes, and are able to optimise growth, on steeper dunes, such that they have to grow less in response to burial than plants that form more shallow dunes. In this thesis, it was shown that the link between the carbon and nitrogen economies of dune plants was pivotal in determining species distributions and survival under extreme environmental conditions. As vast areas of the world’s surface are covered by sand dunes these observations are not just of passing interest.
- 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