In vitro release of ketoprofen from proprietary and extemporaneously manufactured gels
- Tettey-Amlalo, Ralph Nii Okai
- Authors: Tettey-Amlalo, Ralph Nii Okai
- Date: 2005
- Subjects: Transdermal medication , Drug delivery systems , High performance liquid chromatography , Nonsteroidal anti-inflammatory agents , Rheumatoid arthritis -- Treatment
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3797 , http://hdl.handle.net/10962/d1003275 , Transdermal medication , Drug delivery systems , High performance liquid chromatography , Nonsteroidal anti-inflammatory agents , Rheumatoid arthritis -- Treatment
- Description: Ketoprofen is a potent non-steroidal anti-inflammatory drug which is used for the treatment of rheumatoid arthritis. The oral administration of ketoprofen can cause gastric irritation and adverse renal effects. Transdermal delivery of the drug can bypass gastrointestinal disturbances and provide relatively consistent drug concentrations at the site of administration. The release of ketoprofen from proprietary gel products from three different countries was evaluated by comparing the in vitro release profiles. Twenty extemporaneously prepared ketoprofen gel formulations using Carbopol® polymers were manufactured. The effect of polymer, drug concentration, pH and solvent systems on the in vitro release of ketoprofen from these formulations were investigated. The gels were evaluated for drug content and pH. The release of the drug from all the formulations obeyed the Higuchi principle. Two static FDA approved diffusion cells, namely the modified Franz diffusion cell and the European Pharmacopoeia diffusion cell, were compared by measuring the in vitro release rate of ketoprofen from all the gel formulations through a synthetic silicone membrane. High-performance liquid chromatography and ultraviolet spectrophotometric analytical techniques were both used for the analysis of ketoprofen. The validated methods were employed for the determination of ketoprofen in the sample solutions taken from the receptor fluid. Two of the three proprietary products registered under the same manufacturing license exhibited similar results whereas the third product differed significantly. Among the variables investigated, the vehicle pH and solvent composition were found have the most significant effect on the in vitro release of ketoprofen from Carbopol® polymers. The different grades of Carbopol® polymers showed statistically significantly different release kinetics with respect to lag time. When evaluating the proprietary products, both the modified Franz diffusion cell and the European Pharmacopoeia diffusion cell were deemed adequate although higher profiles were generally obtained from the European Pharmacopoeia diffusion cells. Smoother diffusion profiles were obtained from samples analysed by high-performance liquid chromatography than by ultraviolet spectrophotometry in both diffusion cells. Sample solutions taken from Franz diffusion cells and analysed by ultraviolet spectrophotometry also produced smooth diffusion profiles. Erratic and higher diffusion profiles were observed with samples taken from the European Pharmacopoeia diffusion cell and analysed by ultraviolet spectrophotometry. The choice of diffusion cells and analytical procedure in product development must be weighed against the relatively poor reproducibility as observed with the European Pharmacopoeia diffusion cell.
- Full Text:
- Date Issued: 2005
- Authors: Tettey-Amlalo, Ralph Nii Okai
- Date: 2005
- Subjects: Transdermal medication , Drug delivery systems , High performance liquid chromatography , Nonsteroidal anti-inflammatory agents , Rheumatoid arthritis -- Treatment
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3797 , http://hdl.handle.net/10962/d1003275 , Transdermal medication , Drug delivery systems , High performance liquid chromatography , Nonsteroidal anti-inflammatory agents , Rheumatoid arthritis -- Treatment
- Description: Ketoprofen is a potent non-steroidal anti-inflammatory drug which is used for the treatment of rheumatoid arthritis. The oral administration of ketoprofen can cause gastric irritation and adverse renal effects. Transdermal delivery of the drug can bypass gastrointestinal disturbances and provide relatively consistent drug concentrations at the site of administration. The release of ketoprofen from proprietary gel products from three different countries was evaluated by comparing the in vitro release profiles. Twenty extemporaneously prepared ketoprofen gel formulations using Carbopol® polymers were manufactured. The effect of polymer, drug concentration, pH and solvent systems on the in vitro release of ketoprofen from these formulations were investigated. The gels were evaluated for drug content and pH. The release of the drug from all the formulations obeyed the Higuchi principle. Two static FDA approved diffusion cells, namely the modified Franz diffusion cell and the European Pharmacopoeia diffusion cell, were compared by measuring the in vitro release rate of ketoprofen from all the gel formulations through a synthetic silicone membrane. High-performance liquid chromatography and ultraviolet spectrophotometric analytical techniques were both used for the analysis of ketoprofen. The validated methods were employed for the determination of ketoprofen in the sample solutions taken from the receptor fluid. Two of the three proprietary products registered under the same manufacturing license exhibited similar results whereas the third product differed significantly. Among the variables investigated, the vehicle pH and solvent composition were found have the most significant effect on the in vitro release of ketoprofen from Carbopol® polymers. The different grades of Carbopol® polymers showed statistically significantly different release kinetics with respect to lag time. When evaluating the proprietary products, both the modified Franz diffusion cell and the European Pharmacopoeia diffusion cell were deemed adequate although higher profiles were generally obtained from the European Pharmacopoeia diffusion cells. Smoother diffusion profiles were obtained from samples analysed by high-performance liquid chromatography than by ultraviolet spectrophotometry in both diffusion cells. Sample solutions taken from Franz diffusion cells and analysed by ultraviolet spectrophotometry also produced smooth diffusion profiles. Erratic and higher diffusion profiles were observed with samples taken from the European Pharmacopoeia diffusion cell and analysed by ultraviolet spectrophotometry. The choice of diffusion cells and analytical procedure in product development must be weighed against the relatively poor reproducibility as observed with the European Pharmacopoeia diffusion cell.
- Full Text:
- Date Issued: 2005
Incorporating indigenous management in rock art sites in KwaZulu-Natal
- Authors: Ndlovu, Ndukuyakhe
- Date: 2005
- Subjects: Rock paintings -- Drakenberg Mountains , Cave paintings -- Drakensberg Mountains , San (African people) -- Art , Art, Prehistoric -- Drakensberg Mountains , Art, Prehistoric -- South Africa , Heritage tourism -- South Africa
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2089 , http://hdl.handle.net/10962/d1002652 , Rock paintings -- Drakenberg Mountains , Cave paintings -- Drakensberg Mountains , San (African people) -- Art , Art, Prehistoric -- Drakensberg Mountains , Art, Prehistoric -- South Africa , Heritage tourism -- South Africa
- Description: The majestic mountains of the uKhahlamba Drakensberg, formed many millennia ago were home to the Bushmen[footnote 1] or San people. They lived at these mountains for thousands of years before they were colonised by the Bantu speakers and the Europeans. Academic writings for many years have perpetuated the thinking that Bushman people were largely extinct. The dominance of this view in the academic writings was encouraged by historical evidence that Europeans and Bantu speakers hunted and killed Bushmen over the last several centuries. Researchers argue that the extermination of the Bushmen was because they were less human in the eyes of the foreigners, due to cattle raiding. There is still some element of this thinking amongst today’s academics, although research in the last decade is questioning this thinking. The question of whether descendants do exist is relevant to issues of rights of access to ancestral sacred sites, in particular rock art sites. At present, access to rock art sites is granted on qualification as an authentic fee-paying tourist (or affordability) rather than on group rights to a cultural heritage resource (cultural rights). Based on this, I argue that access to rock art sites is based on qualification rather than by right. This is largely driven by an approach that emphasises the physical conservation and financial sustainability of a site, rather than its spiritual maintenance. It has become clear that the interests in rock art by tourists and Bushman descendants are distinct from each other. Tourists have an aesthetic significance for rock art while Bushmen descendants have a spiritual significance for the paintings. Beyond any doubt, the physically based and financially driven approach has brought new challenges to today’s Bushmen descendants, whom in reaffirming their identities now have a new challenge to overcome. Not only are the rock art sites physically threatened but also they have lost much of their spiritual powers. Their fate lies in the hands of heritage officers who must determine access rights to the painted shelters. Both the National Heritage Resources Act and the KwaZulu-Natal Heritage Act acknowledge living heritage. However, the existence of this heritage is judged against the physical approach to rock art management. If the practises of descendants are perceived to be a threat to the rock art, they will not be approved. The case of the Duma is a classic example. Prior to the ritual ceremony at Game Pass Shelter, Kamberg, they were informed of the minimum standards for opening a rock art site to public and rules of how people should behave while visiting painted shelters. While it was evident that there are problems with the two approaches, the spiritual and physical approach, discussed in the thesis, it is important that solutions are identified. I do not believe that one approach on its own will be good enough, for reasons discussed in the thesis. Instead, the two approaches should be implemented together to compliment each other by identifying common grounds. I provide strategies as to how I believe that such a common ground can be reached. In addition, I provide my own analytical thinking as to how these strategies can be achieved. There is no general consensus over which term is appropriate. Both terms are considered by some academics to be derogatory or pejorative (Chennels 2003). San means vagabond and was given to the Bushmen by Khoi-Khoi people, because they considered themselves of a better social class, as they had domesticated animals and were more sedentary than Bushmen. However, according to WIMSA (Thoma 2003) the word San is derived from the Hai||om language meaning “people who gather”. It is normally written Saan but it has been accepted to write San. In 1993 the San requested to be called San when referred to as an entire group. If one refers to individual people/groups they like to be called by their language and cultural name i.e. Khwe, !Kung, !Xun, Ju|’hoansi, ‡Khomani, N|u, |’Auni, Hai||om, etc In this thesis, Bushmen is a preferred term, because it is a better-known term among the people who are central to this study. It is used without any insulting connotations attached to the term.
- Full Text:
- Date Issued: 2005
- Authors: Ndlovu, Ndukuyakhe
- Date: 2005
- Subjects: Rock paintings -- Drakenberg Mountains , Cave paintings -- Drakensberg Mountains , San (African people) -- Art , Art, Prehistoric -- Drakensberg Mountains , Art, Prehistoric -- South Africa , Heritage tourism -- South Africa
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2089 , http://hdl.handle.net/10962/d1002652 , Rock paintings -- Drakenberg Mountains , Cave paintings -- Drakensberg Mountains , San (African people) -- Art , Art, Prehistoric -- Drakensberg Mountains , Art, Prehistoric -- South Africa , Heritage tourism -- South Africa
- Description: The majestic mountains of the uKhahlamba Drakensberg, formed many millennia ago were home to the Bushmen[footnote 1] or San people. They lived at these mountains for thousands of years before they were colonised by the Bantu speakers and the Europeans. Academic writings for many years have perpetuated the thinking that Bushman people were largely extinct. The dominance of this view in the academic writings was encouraged by historical evidence that Europeans and Bantu speakers hunted and killed Bushmen over the last several centuries. Researchers argue that the extermination of the Bushmen was because they were less human in the eyes of the foreigners, due to cattle raiding. There is still some element of this thinking amongst today’s academics, although research in the last decade is questioning this thinking. The question of whether descendants do exist is relevant to issues of rights of access to ancestral sacred sites, in particular rock art sites. At present, access to rock art sites is granted on qualification as an authentic fee-paying tourist (or affordability) rather than on group rights to a cultural heritage resource (cultural rights). Based on this, I argue that access to rock art sites is based on qualification rather than by right. This is largely driven by an approach that emphasises the physical conservation and financial sustainability of a site, rather than its spiritual maintenance. It has become clear that the interests in rock art by tourists and Bushman descendants are distinct from each other. Tourists have an aesthetic significance for rock art while Bushmen descendants have a spiritual significance for the paintings. Beyond any doubt, the physically based and financially driven approach has brought new challenges to today’s Bushmen descendants, whom in reaffirming their identities now have a new challenge to overcome. Not only are the rock art sites physically threatened but also they have lost much of their spiritual powers. Their fate lies in the hands of heritage officers who must determine access rights to the painted shelters. Both the National Heritage Resources Act and the KwaZulu-Natal Heritage Act acknowledge living heritage. However, the existence of this heritage is judged against the physical approach to rock art management. If the practises of descendants are perceived to be a threat to the rock art, they will not be approved. The case of the Duma is a classic example. Prior to the ritual ceremony at Game Pass Shelter, Kamberg, they were informed of the minimum standards for opening a rock art site to public and rules of how people should behave while visiting painted shelters. While it was evident that there are problems with the two approaches, the spiritual and physical approach, discussed in the thesis, it is important that solutions are identified. I do not believe that one approach on its own will be good enough, for reasons discussed in the thesis. Instead, the two approaches should be implemented together to compliment each other by identifying common grounds. I provide strategies as to how I believe that such a common ground can be reached. In addition, I provide my own analytical thinking as to how these strategies can be achieved. There is no general consensus over which term is appropriate. Both terms are considered by some academics to be derogatory or pejorative (Chennels 2003). San means vagabond and was given to the Bushmen by Khoi-Khoi people, because they considered themselves of a better social class, as they had domesticated animals and were more sedentary than Bushmen. However, according to WIMSA (Thoma 2003) the word San is derived from the Hai||om language meaning “people who gather”. It is normally written Saan but it has been accepted to write San. In 1993 the San requested to be called San when referred to as an entire group. If one refers to individual people/groups they like to be called by their language and cultural name i.e. Khwe, !Kung, !Xun, Ju|’hoansi, ‡Khomani, N|u, |’Auni, Hai||om, etc In this thesis, Bushmen is a preferred term, because it is a better-known term among the people who are central to this study. It is used without any insulting connotations attached to the term.
- Full Text:
- Date Issued: 2005
Increasing competitiveness through the enhancement of logistics processes in the South African automotive industry
- Authors: Njokweni, Thobela
- Date: 2005
- Subjects: Business logistics , Automobile industry and trade -- South Africa , Competition, International
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10939 , http://hdl.handle.net/10948/418 , Business logistics , Automobile industry and trade -- South Africa , Competition, International
- Description: Logistics has become one of the automotive industry's most crucial sub-sectors. Previously, logistics had to step aside to make way for production considerations. Today it is regarded as being every bit as crucial as production in the global village. Advancement of logistics in South Africa is crucial because original equipment manufacturers are producing to developed world standards but are having to cope with low developing world logistics standards. The logistics processes that need to be enhanced in order for the South African automotive industry to be more competitive were investigated. To examine the main problem, three sub-problems were identified. The first sub-problem that has been identified dealt with logistics processes that will enhance the competitive advantage of the South African automotive industry. The second sub-problems looked at key logistics opportunities and threats to the environment in which South African motor manufactures trade. They were investigated by assessing the nature of the South African motor manufacturing industry. Finally, the third sub-problem investigated conclusions that can be arrived at concerning the appropriateness and strategic value of the analysis.
- Full Text:
- Date Issued: 2005
- Authors: Njokweni, Thobela
- Date: 2005
- Subjects: Business logistics , Automobile industry and trade -- South Africa , Competition, International
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10939 , http://hdl.handle.net/10948/418 , Business logistics , Automobile industry and trade -- South Africa , Competition, International
- Description: Logistics has become one of the automotive industry's most crucial sub-sectors. Previously, logistics had to step aside to make way for production considerations. Today it is regarded as being every bit as crucial as production in the global village. Advancement of logistics in South Africa is crucial because original equipment manufacturers are producing to developed world standards but are having to cope with low developing world logistics standards. The logistics processes that need to be enhanced in order for the South African automotive industry to be more competitive were investigated. To examine the main problem, three sub-problems were identified. The first sub-problem that has been identified dealt with logistics processes that will enhance the competitive advantage of the South African automotive industry. The second sub-problems looked at key logistics opportunities and threats to the environment in which South African motor manufactures trade. They were investigated by assessing the nature of the South African motor manufacturing industry. Finally, the third sub-problem investigated conclusions that can be arrived at concerning the appropriateness and strategic value of the analysis.
- Full Text:
- Date Issued: 2005
Inspectors of education's perceptions of female principalship in the Rundu region of Namibia
- Authors: Kawana, Irene
- Date: 2005
- Subjects: Women school principals -- Namibia -- Rundu , Educational leadership -- Namibia -- Rundu , Sex discrimination in employment -- Namibia , School supervisors -- Namibia -- Attitudes
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:2006 , http://hdl.handle.net/10962/d1015746
- Description: While women constitute more than 51% of the population and far outnumber men in teaching positions in Namibia, very few occupy positions of leadership. Male candidates are still favoured for top positions, thereby denying women the chance to gain entrance to these positions. One of the reasons for this imbalance seems to be that, in spite of conscious political effort and legislation, women may still be perceived as less effective leaders than men. This research focused on leadership in education, in particular school principals, and explored the perceptions of female principalship held by school inspectors. Three school inspectors from the Rundu Education Region were purposefully selected and interviewed. Inspectors were selected on the grounds of their considerable influence in the selection and appointment of school principals. The study found that these inspectors favour school principals who show commitment to their work, have good interpersonal working relationships, are caring, good listeners, visionary and produce good results. The inspectors attribute female principals’ success to their traditionally perceived characteristics, such as caring leadership and ability to develop good human relations. Instead of perceiving these qualities as professionally negative (as is sometimes argued in the literature) the inspectors see them as indisputable assets to leadership. The respondents acknowledge the cultural stereotyping that may have influenced male attitudes to women in the past, but argue that good leadership is not specific to gender, but part of the qualities a person possesses, regardless of sex. This study concludes that, contrary to what has been reported in many studies, these inspectors perceive women principals as effective – equal to their male counterparts or sometimes even more effective - because they are caring, well organized and good at communicating and establishing relations with others. Though these qualities are different from the traditional masculine qualities which include independence and emotional strength, the respondents recognize and legitimize them as preferred qualities in current effective leadership practice.
- Full Text:
- Date Issued: 2005
- Authors: Kawana, Irene
- Date: 2005
- Subjects: Women school principals -- Namibia -- Rundu , Educational leadership -- Namibia -- Rundu , Sex discrimination in employment -- Namibia , School supervisors -- Namibia -- Attitudes
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:2006 , http://hdl.handle.net/10962/d1015746
- Description: While women constitute more than 51% of the population and far outnumber men in teaching positions in Namibia, very few occupy positions of leadership. Male candidates are still favoured for top positions, thereby denying women the chance to gain entrance to these positions. One of the reasons for this imbalance seems to be that, in spite of conscious political effort and legislation, women may still be perceived as less effective leaders than men. This research focused on leadership in education, in particular school principals, and explored the perceptions of female principalship held by school inspectors. Three school inspectors from the Rundu Education Region were purposefully selected and interviewed. Inspectors were selected on the grounds of their considerable influence in the selection and appointment of school principals. The study found that these inspectors favour school principals who show commitment to their work, have good interpersonal working relationships, are caring, good listeners, visionary and produce good results. The inspectors attribute female principals’ success to their traditionally perceived characteristics, such as caring leadership and ability to develop good human relations. Instead of perceiving these qualities as professionally negative (as is sometimes argued in the literature) the inspectors see them as indisputable assets to leadership. The respondents acknowledge the cultural stereotyping that may have influenced male attitudes to women in the past, but argue that good leadership is not specific to gender, but part of the qualities a person possesses, regardless of sex. This study concludes that, contrary to what has been reported in many studies, these inspectors perceive women principals as effective – equal to their male counterparts or sometimes even more effective - because they are caring, well organized and good at communicating and establishing relations with others. Though these qualities are different from the traditional masculine qualities which include independence and emotional strength, the respondents recognize and legitimize them as preferred qualities in current effective leadership practice.
- Full Text:
- Date Issued: 2005
Institutional change and ecosystem dynamics in the communal areas around Mt Coke State Forest, Eastern Cape, South Africa
- Authors: Cundill, Georgina
- Date: 2005
- Subjects: Biodiversity -- South Africa -- Eastern Cape , Ecosystem management -- South Africa -- Eastern Cape , Natural resources -- Management -- South Africa -- Eastern Cape , Sustainable agriculture -- South Africa -- Eastern Cape , Sustainable development -- South Africa -- Eastern Cape , Rural development -- South Africa -- Eastern Cape , Nature conservation -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:4746 , http://hdl.handle.net/10962/d1006959 , Biodiversity -- South Africa -- Eastern Cape , Ecosystem management -- South Africa -- Eastern Cape , Natural resources -- Management -- South Africa -- Eastern Cape , Sustainable agriculture -- South Africa -- Eastern Cape , Sustainable development -- South Africa -- Eastern Cape , Rural development -- South Africa -- Eastern Cape , Nature conservation -- South Africa -- Eastern Cape
- Description: Through a combination of theoretical discussion and case study analysis from two villages in the Eastern Cape Province, South Africa, this thesis explores the relationship between institutional change and ecosystem dynamics through a multi-scale approach that combines local and scientific knowledge. Several conceptual approaches were combined in this study. These included; the Resilience perspective, the Sustainable Rural Livelihoods approach, the Millennium Assessment framework and principles, and the Environmental Entitlements approach. Various participatory research techniques were employed which combined with GIS technologies, existing data sets, and historical records. Common pool resource areas are social spaces, where local values attached to resources are institutionally mediated, politically nuanced, economically interpreted and historically situated. Political driving forces at various scales have played a disproportionate role in local level institutional functioning in the case study area. In particular, inappropriate state-lead interventions into land use planning have weakened local level institutions, and have reduced the ability of the linked social-ecological system to cope with change and uncertainty. People and ecosystems become more vulnerable when driving forces such as political upheaval, economic depression and drought over-lap. However, rural people are not mere spectators in the face of these driving forces; they respond both reactively and proactively to ensure resilience to change and uncertainty. Ecosystems at Mt Coke play a key role during times of crisis in rural livelihoods. These ecosystems have undergone various short-term cyclical changes largely in response to rainfall fluctuations, and some longer-term changes linked to political events and trends that have affected management practices and local institutions over time. Orthodox ecological interpretations of ecosystem change appear to ignore four key factors identified in this study: 1) the role of institutions in shaping access to resources, 2) the demand for resources in rural livelihoods, 3) the dynamic interaction between social and natural systems, and 4) the interaction between social and natural systems across scales of analysis. The future of common pool resource management lies in the combination of local and scientific knowledge through an adaptive management approach that encourages learning and adaptation in local level institutional structures.
- Full Text:
- Date Issued: 2005
- Authors: Cundill, Georgina
- Date: 2005
- Subjects: Biodiversity -- South Africa -- Eastern Cape , Ecosystem management -- South Africa -- Eastern Cape , Natural resources -- Management -- South Africa -- Eastern Cape , Sustainable agriculture -- South Africa -- Eastern Cape , Sustainable development -- South Africa -- Eastern Cape , Rural development -- South Africa -- Eastern Cape , Nature conservation -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:4746 , http://hdl.handle.net/10962/d1006959 , Biodiversity -- South Africa -- Eastern Cape , Ecosystem management -- South Africa -- Eastern Cape , Natural resources -- Management -- South Africa -- Eastern Cape , Sustainable agriculture -- South Africa -- Eastern Cape , Sustainable development -- South Africa -- Eastern Cape , Rural development -- South Africa -- Eastern Cape , Nature conservation -- South Africa -- Eastern Cape
- Description: Through a combination of theoretical discussion and case study analysis from two villages in the Eastern Cape Province, South Africa, this thesis explores the relationship between institutional change and ecosystem dynamics through a multi-scale approach that combines local and scientific knowledge. Several conceptual approaches were combined in this study. These included; the Resilience perspective, the Sustainable Rural Livelihoods approach, the Millennium Assessment framework and principles, and the Environmental Entitlements approach. Various participatory research techniques were employed which combined with GIS technologies, existing data sets, and historical records. Common pool resource areas are social spaces, where local values attached to resources are institutionally mediated, politically nuanced, economically interpreted and historically situated. Political driving forces at various scales have played a disproportionate role in local level institutional functioning in the case study area. In particular, inappropriate state-lead interventions into land use planning have weakened local level institutions, and have reduced the ability of the linked social-ecological system to cope with change and uncertainty. People and ecosystems become more vulnerable when driving forces such as political upheaval, economic depression and drought over-lap. However, rural people are not mere spectators in the face of these driving forces; they respond both reactively and proactively to ensure resilience to change and uncertainty. Ecosystems at Mt Coke play a key role during times of crisis in rural livelihoods. These ecosystems have undergone various short-term cyclical changes largely in response to rainfall fluctuations, and some longer-term changes linked to political events and trends that have affected management practices and local institutions over time. Orthodox ecological interpretations of ecosystem change appear to ignore four key factors identified in this study: 1) the role of institutions in shaping access to resources, 2) the demand for resources in rural livelihoods, 3) the dynamic interaction between social and natural systems, and 4) the interaction between social and natural systems across scales of analysis. The future of common pool resource management lies in the combination of local and scientific knowledge through an adaptive management approach that encourages learning and adaptation in local level institutional structures.
- Full Text:
- Date Issued: 2005
Interest rate behaviour in a more transparent South African monetary policy environment
- Authors: Ballim, Goolam Hoosen
- Date: 2005
- Subjects: South African Reserve Bank , Monetary policy -- South Africa , Banks and banking -- South Africa , Interest rates -- South Africa , South Africa -- Economic policy , South Africa -- Economic conditions
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:1034 , http://hdl.handle.net/10962/d1004462 , South African Reserve Bank , Monetary policy -- South Africa , Banks and banking -- South Africa , Interest rates -- South Africa , South Africa -- Economic policy , South Africa -- Economic conditions
- Description: South Africa introduced inflation targeting as a monetary policy framework in 2000. This marked a sizable shift in monetary policy management from the previous "eclectic" approach and the explicit focus on M3 money supply before that. The study appraises the effectiveness of monetary policy under this new dispensation. However, the analysis does not centre on inflation outcomes, which can be a measure of effectiveness because they are the overriding objective of the South African Reserve Bank in effect, it is possible to have a target-friendly inflation rate for a length of time despite monetary policy that is ambiguous and encourages unpredictability in market interest rates. However, persistent policy opaqueness can, over time, damage a favourable inflation scenario. For instance, if the public is unsure about the Reserve Bank's desired inflation target, price setting in the wage and goods markets may eventually produce an inflation outcome that is higher than the Bank may have intended. Rather, this study adjudicates the effectiveness of monetary policy within the context of policy transparency, which is an intrinsic part of the inflation targeting framework. The study looks at the extent to which monetary policy transparency has enhanced both the anticipatory nature of the market's response to policy actions and the force that policy has on all interest rates in the financial system, particularly long-term rates. These concepts are important because through the transmission mechanism of monetary policy, the more deft market participants are at anticipating future Reserve Bank policy the greater the Bank's ability to steady the economy before the actual policy event. With the aid of regression models to estimate the response of market rates to policy changes, the results show that there is significant movement in market rates in anticipation of policy action, rather than on the day of the event or the day after. Indeed, the estimates for market rates movement on the day of and even the day after the policy action are generally minute. For instance, the R157 long-term government bond yield changes by a significant 41 basis points in response to a one percentage point change in the Reserve Bank's benchmark repo rate in the period between the last policy action and the day preceding the current action. In contrast, the R157 bond yield changes by an insignificant 2 basis points on the day of the current repo rate change and about 1 basis point the day after the current change. The results point to a robust relationship between policy transparency and the market's ability to foresee rate action. If this were not the case, it is likely that there would be persistent market surprise and, hence, noticeable movement in interest rates on the day of the rate action and perhaps even the day after. Another important observation is that monetary policy impacts significantly on both short- and long-term market rates. Again, certifying the robustness of monetary policy under the inflation targeting regime
- Full Text:
- Date Issued: 2005
- Authors: Ballim, Goolam Hoosen
- Date: 2005
- Subjects: South African Reserve Bank , Monetary policy -- South Africa , Banks and banking -- South Africa , Interest rates -- South Africa , South Africa -- Economic policy , South Africa -- Economic conditions
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:1034 , http://hdl.handle.net/10962/d1004462 , South African Reserve Bank , Monetary policy -- South Africa , Banks and banking -- South Africa , Interest rates -- South Africa , South Africa -- Economic policy , South Africa -- Economic conditions
- Description: South Africa introduced inflation targeting as a monetary policy framework in 2000. This marked a sizable shift in monetary policy management from the previous "eclectic" approach and the explicit focus on M3 money supply before that. The study appraises the effectiveness of monetary policy under this new dispensation. However, the analysis does not centre on inflation outcomes, which can be a measure of effectiveness because they are the overriding objective of the South African Reserve Bank in effect, it is possible to have a target-friendly inflation rate for a length of time despite monetary policy that is ambiguous and encourages unpredictability in market interest rates. However, persistent policy opaqueness can, over time, damage a favourable inflation scenario. For instance, if the public is unsure about the Reserve Bank's desired inflation target, price setting in the wage and goods markets may eventually produce an inflation outcome that is higher than the Bank may have intended. Rather, this study adjudicates the effectiveness of monetary policy within the context of policy transparency, which is an intrinsic part of the inflation targeting framework. The study looks at the extent to which monetary policy transparency has enhanced both the anticipatory nature of the market's response to policy actions and the force that policy has on all interest rates in the financial system, particularly long-term rates. These concepts are important because through the transmission mechanism of monetary policy, the more deft market participants are at anticipating future Reserve Bank policy the greater the Bank's ability to steady the economy before the actual policy event. With the aid of regression models to estimate the response of market rates to policy changes, the results show that there is significant movement in market rates in anticipation of policy action, rather than on the day of the event or the day after. Indeed, the estimates for market rates movement on the day of and even the day after the policy action are generally minute. For instance, the R157 long-term government bond yield changes by a significant 41 basis points in response to a one percentage point change in the Reserve Bank's benchmark repo rate in the period between the last policy action and the day preceding the current action. In contrast, the R157 bond yield changes by an insignificant 2 basis points on the day of the current repo rate change and about 1 basis point the day after the current change. The results point to a robust relationship between policy transparency and the market's ability to foresee rate action. If this were not the case, it is likely that there would be persistent market surprise and, hence, noticeable movement in interest rates on the day of the rate action and perhaps even the day after. Another important observation is that monetary policy impacts significantly on both short- and long-term market rates. Again, certifying the robustness of monetary policy under the inflation targeting regime
- Full Text:
- Date Issued: 2005
International relations and change: a Kuhnian interpretation
- Authors: Schoeman, Jacobus
- Date: 2005
- Subjects: Kuhn, Thomas S Kuhn, Thomas S -- Criticism and interpretation International relations International relations -- Philosophy Knowledge, Theory of
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2830 , http://hdl.handle.net/10962/d1003040
- Description: Using notions of change developed by Thomas Kuhn, the thesis argues that the rise of globalisation and the end of the Cold War presented the Westphalian or state-centric paradigm of international relations with a Kuhnian paradigm “crisis”. As a result, both the theory and the practice of international relations are in the midst of (what Kuhn calls) a “paradigm shift”. Emerging from this shift is (what is described in this work as) “Access World” and “Denial World” – a particular global configuration of the practice of international relations. Kuhn’s idea of “incommensurability” seems to typify the relationship between the two components of this bifurcated configuration of the international. Both intellectual risk-taking and political courage are required if the ontological struggle raging between “Access World” and “Denial World” is to be settled. This will pave the way for a new paradigm to emerge. Kuhn provides us with the insight that, to achieve this ontological breakthrough, a fundamental change in our vision of the discipline of International Relations, but also of the world of everyday international relations, is required. This entails recasting the study of International Relations as an emancipatory project and by recognising the centrality of human beings in the practice of international relations. Only if this is done, will we be able to arrive at a cosmopolitan political bargain that is appropriate for the 21st century.
- Full Text:
- Date Issued: 2005
- Authors: Schoeman, Jacobus
- Date: 2005
- Subjects: Kuhn, Thomas S Kuhn, Thomas S -- Criticism and interpretation International relations International relations -- Philosophy Knowledge, Theory of
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2830 , http://hdl.handle.net/10962/d1003040
- Description: Using notions of change developed by Thomas Kuhn, the thesis argues that the rise of globalisation and the end of the Cold War presented the Westphalian or state-centric paradigm of international relations with a Kuhnian paradigm “crisis”. As a result, both the theory and the practice of international relations are in the midst of (what Kuhn calls) a “paradigm shift”. Emerging from this shift is (what is described in this work as) “Access World” and “Denial World” – a particular global configuration of the practice of international relations. Kuhn’s idea of “incommensurability” seems to typify the relationship between the two components of this bifurcated configuration of the international. Both intellectual risk-taking and political courage are required if the ontological struggle raging between “Access World” and “Denial World” is to be settled. This will pave the way for a new paradigm to emerge. Kuhn provides us with the insight that, to achieve this ontological breakthrough, a fundamental change in our vision of the discipline of International Relations, but also of the world of everyday international relations, is required. This entails recasting the study of International Relations as an emancipatory project and by recognising the centrality of human beings in the practice of international relations. Only if this is done, will we be able to arrive at a cosmopolitan political bargain that is appropriate for the 21st century.
- Full Text:
- Date Issued: 2005
Intraspecific comparison of Phanerochaete chrysosporium strains peroxidase production, pollutant degradation and mycelial differentiation
- Authors: Fraser, Sheena Janet
- Date: 2005
- Subjects: Phanerochaete Pollutants -- Biodegradation Lignin -- Biodegradation Bioremediation Peroxidase Fungi -- Differentiation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3964 , http://hdl.handle.net/10962/d1004023
- Description: The wood-degrading basidiomycete, Phanerochaete chrysosporium, has been studied as a model organism in elucidating the mechanisms and pathways enabling this white-rot fungus to degrade recalcitrant lignin. These same mechanisms are implicated in the mineralisation of environmentally persistent, toxic phenolic chemicals. For this reason, P. chrysosporium has been exploited in a number of environmentally sound technologies, including the degradation of the indigestible lignin component in agricultural waste for the generation of digestible animal feedstocks or high sugar content raw materials for ethanol production; brightening processes in the pulp and paper industry; the detoxification and decolourisation of industrial effluents; and the bioremediation of hazardous waste sites. The improvement of these technologies is dependant on ongoing research involving strain selection, strain development using genetic engineering approaches and process development. Strain improvement using non-recombinant methods is beneficial in that it does not limit the inherent robustness observed amongst natural variants. In this research, through a breeding programme, ten P.chrysosporium sibling strains were screened for variable ligninase activities and pollutant degradation capabilities in order to further describe previously identified differences between these organisms. A conventional stationary liquid culture technique was effectively miniaturised from 10 ml flask cultures to a 96-well microtitre plate format, for the assessment of multigenic traits amongst sibling strains. Using the 96-well microtitre plate method, the relationships between P. chrysosporium growth kinetics, peroxidase production, pollutant sensitivity and pollutant degradation was explored. Significant correlations were primarily associated with P. chrysosporium growth [P < 0.05]. Percentage p-cresol removal and tannic acid tolerance were both correlated with a shorter lag phase in growth [tannic acid: r = 0.7698, P < 0.05; p-cresol: r = 0.7584, P < 0.05] and lower stationary phase biomass levels [tannic acid: r = 0.8177, P < 0.05; p-cresol: r = 0.7803, P < 0.05]. A significant correlation (linear relationship) was also detected between percentage Poly-R478 decolourisation and time of onset of MnP [r = 0.9689, P < 0.001]. No correlation was observed between dye decolourisation, p-cresol degradation, lignin degradation and lignin peroxidase (LiP) or manganese peroxidase (MnP) activities [P > 0.05]. These results imply that differences in the biosynthetic pathways for biomass accumulation in sibling strains play a significant role in the intraspecific variation observed in pollutant sensitivity, pollutant degradation, and enzyme production. Categorical analysis of intraspecific differences was assessed according to four criterions. These included growth, extracellular peroxidase activities, tolerance to toxic pollutants and the biodegradation of model pollutants. Sibling strains showing the most variable responses in three or more of the selective criterion were recommended for further studies. These strains include P. chrysosporium ME446, BS 2.52, BS 13, BS 17, BS 18, and BS 24. Interestingly, BS 2.52 (a dikaryotic strain generating from the crossing of two haploid progeny) showed significantly lower degradation capabilities than the wildtype parent strain ME446. The inherited variability observed between sibling strains is to be further explored through proteome and transcriptome analysis and genetic linkage studies aimed at describing the mechanisms or pathways conferring tolerance to or degradation of environmental pollutants. In examining fewer organisms at this next level, the number of replicates examined can be increased and thus the power of detection of experimental procedures improved, enabling the detection of multigenic traits amongst genetically related organisms. Growth was shown to play a significant role in the intraspecific differences detected in pollutant sensitivity and degradation between sibling strains. Little is known about the mechanism of growth and differentiation, or the role of differentiation in regulating the lignolytic activity in this organism. The membrane gradostat bioreactor and a unique plug-flow membrane bioreactor were evaluated as novel tools with which to further explore the relationship between secondary metabolism, pollutant degradation and biofilm development in sibling strains. High yield MnP production at levels as high as 1478.8 U.l-1 was achieved using a laboratory scale membrane gradostat bioreactor. Furthermore, extensive mycelial differentiation and tissue formation are reported for P. chrysosporium in both the membrane gradostat bioreactor and plug-flow membrane bioreactor. Intraspecific differences in the extent of this differentiation were observed in strains ME446, BS 13, BS 17 and BS 26 cultured using the membrane gradostat bioreactor, highlighting the potential of these techniques as a platform for future strain improvement strategies.
- Full Text:
- Date Issued: 2005
- Authors: Fraser, Sheena Janet
- Date: 2005
- Subjects: Phanerochaete Pollutants -- Biodegradation Lignin -- Biodegradation Bioremediation Peroxidase Fungi -- Differentiation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3964 , http://hdl.handle.net/10962/d1004023
- Description: The wood-degrading basidiomycete, Phanerochaete chrysosporium, has been studied as a model organism in elucidating the mechanisms and pathways enabling this white-rot fungus to degrade recalcitrant lignin. These same mechanisms are implicated in the mineralisation of environmentally persistent, toxic phenolic chemicals. For this reason, P. chrysosporium has been exploited in a number of environmentally sound technologies, including the degradation of the indigestible lignin component in agricultural waste for the generation of digestible animal feedstocks or high sugar content raw materials for ethanol production; brightening processes in the pulp and paper industry; the detoxification and decolourisation of industrial effluents; and the bioremediation of hazardous waste sites. The improvement of these technologies is dependant on ongoing research involving strain selection, strain development using genetic engineering approaches and process development. Strain improvement using non-recombinant methods is beneficial in that it does not limit the inherent robustness observed amongst natural variants. In this research, through a breeding programme, ten P.chrysosporium sibling strains were screened for variable ligninase activities and pollutant degradation capabilities in order to further describe previously identified differences between these organisms. A conventional stationary liquid culture technique was effectively miniaturised from 10 ml flask cultures to a 96-well microtitre plate format, for the assessment of multigenic traits amongst sibling strains. Using the 96-well microtitre plate method, the relationships between P. chrysosporium growth kinetics, peroxidase production, pollutant sensitivity and pollutant degradation was explored. Significant correlations were primarily associated with P. chrysosporium growth [P < 0.05]. Percentage p-cresol removal and tannic acid tolerance were both correlated with a shorter lag phase in growth [tannic acid: r = 0.7698, P < 0.05; p-cresol: r = 0.7584, P < 0.05] and lower stationary phase biomass levels [tannic acid: r = 0.8177, P < 0.05; p-cresol: r = 0.7803, P < 0.05]. A significant correlation (linear relationship) was also detected between percentage Poly-R478 decolourisation and time of onset of MnP [r = 0.9689, P < 0.001]. No correlation was observed between dye decolourisation, p-cresol degradation, lignin degradation and lignin peroxidase (LiP) or manganese peroxidase (MnP) activities [P > 0.05]. These results imply that differences in the biosynthetic pathways for biomass accumulation in sibling strains play a significant role in the intraspecific variation observed in pollutant sensitivity, pollutant degradation, and enzyme production. Categorical analysis of intraspecific differences was assessed according to four criterions. These included growth, extracellular peroxidase activities, tolerance to toxic pollutants and the biodegradation of model pollutants. Sibling strains showing the most variable responses in three or more of the selective criterion were recommended for further studies. These strains include P. chrysosporium ME446, BS 2.52, BS 13, BS 17, BS 18, and BS 24. Interestingly, BS 2.52 (a dikaryotic strain generating from the crossing of two haploid progeny) showed significantly lower degradation capabilities than the wildtype parent strain ME446. The inherited variability observed between sibling strains is to be further explored through proteome and transcriptome analysis and genetic linkage studies aimed at describing the mechanisms or pathways conferring tolerance to or degradation of environmental pollutants. In examining fewer organisms at this next level, the number of replicates examined can be increased and thus the power of detection of experimental procedures improved, enabling the detection of multigenic traits amongst genetically related organisms. Growth was shown to play a significant role in the intraspecific differences detected in pollutant sensitivity and degradation between sibling strains. Little is known about the mechanism of growth and differentiation, or the role of differentiation in regulating the lignolytic activity in this organism. The membrane gradostat bioreactor and a unique plug-flow membrane bioreactor were evaluated as novel tools with which to further explore the relationship between secondary metabolism, pollutant degradation and biofilm development in sibling strains. High yield MnP production at levels as high as 1478.8 U.l-1 was achieved using a laboratory scale membrane gradostat bioreactor. Furthermore, extensive mycelial differentiation and tissue formation are reported for P. chrysosporium in both the membrane gradostat bioreactor and plug-flow membrane bioreactor. Intraspecific differences in the extent of this differentiation were observed in strains ME446, BS 13, BS 17 and BS 26 cultured using the membrane gradostat bioreactor, highlighting the potential of these techniques as a platform for future strain improvement strategies.
- Full Text:
- Date Issued: 2005
Introducing hippocratic log files for personal privacy control
- Authors: Rutherford, Andrew
- Date: 2005
- Subjects: Computer security , Internet -- Security measures
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:9743 , http://hdl.handle.net/10948/171 , Computer security , Internet -- Security measures
- Description: The rapid growth of the Internet has served to intensify existing privacy concerns of the individual, to the point that privacy is the number one concern amongst Internet users today. Tools exist that can provide users with a choice of anonymity or pseudonymity. However, many Web transactions require the release of personally identifying information, thus rendering such tools infeasible in many instances. Since it is then a given that users are often required to release personal information, which could be recorded, it follows that they require a greater degree of control over the information they release. Hippocratic databases, designed by Agrawal, Kiernan, Srikant, and Xu (2002), aim to give users greater control over information stored in a data- base. Their design was inspired by the medical Hippocratic oath, and makes data privacy protection a fundamental responsibility of the database itself. To achieve the privacy of data, Hippocratic databases are governed by 10 key privacy principles. This dissertation argues, that asides from a few challenges, the 10 prin- ciples of Hippocratic databases can be applied to log ¯les. This argument is supported by presenting a high-level functional view of a Hippocratic log file architecture. This architecture focuses on issues that highlight the con- trol users gain over their personal information that is collected in log files. By presenting a layered view of the aforementioned architecture, it was, fur- thermore, possible to provide greater insight into the major processes that would be at work in a Hippocratic log file implementation. An exploratory prototype served to understand and demonstrate certain of the architectural components of Hippocratic log files. This dissertation, thus, makes a contribution to the ideal of providing users with greater control over their personal information, by proposing the use of Hippocratic logfiles.
- Full Text:
- Date Issued: 2005
- Authors: Rutherford, Andrew
- Date: 2005
- Subjects: Computer security , Internet -- Security measures
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:9743 , http://hdl.handle.net/10948/171 , Computer security , Internet -- Security measures
- Description: The rapid growth of the Internet has served to intensify existing privacy concerns of the individual, to the point that privacy is the number one concern amongst Internet users today. Tools exist that can provide users with a choice of anonymity or pseudonymity. However, many Web transactions require the release of personally identifying information, thus rendering such tools infeasible in many instances. Since it is then a given that users are often required to release personal information, which could be recorded, it follows that they require a greater degree of control over the information they release. Hippocratic databases, designed by Agrawal, Kiernan, Srikant, and Xu (2002), aim to give users greater control over information stored in a data- base. Their design was inspired by the medical Hippocratic oath, and makes data privacy protection a fundamental responsibility of the database itself. To achieve the privacy of data, Hippocratic databases are governed by 10 key privacy principles. This dissertation argues, that asides from a few challenges, the 10 prin- ciples of Hippocratic databases can be applied to log ¯les. This argument is supported by presenting a high-level functional view of a Hippocratic log file architecture. This architecture focuses on issues that highlight the con- trol users gain over their personal information that is collected in log files. By presenting a layered view of the aforementioned architecture, it was, fur- thermore, possible to provide greater insight into the major processes that would be at work in a Hippocratic log file implementation. An exploratory prototype served to understand and demonstrate certain of the architectural components of Hippocratic log files. This dissertation, thus, makes a contribution to the ideal of providing users with greater control over their personal information, by proposing the use of Hippocratic logfiles.
- Full Text:
- Date Issued: 2005
Investigating call control using MGCP in conjuction with SIP and H.323
- Authors: Jacobs, Ashley
- Date: 2005 , 2005-03-14
- Subjects: Communication -- Technological innovations , Digital telephone systems , Computer networks , Computer network protocols , Internet telephony
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4631 , http://hdl.handle.net/10962/d1006516 , Communication -- Technological innovations , Digital telephone systems , Computer networks , Computer network protocols , Internet telephony
- Description: Telephony used to mean using a telephone to call another telephone on the Public Switched Telephone Network (PSTN), and data networks were used purely to allow computers to communicate. However, with the advent of the Internet, telephony services have been extended to run on data networks. Telephone calls within the IP network are known as Voice over IP. These calls are carried by a number of protocols, with the most popular ones currently being Session Initiation Protocol (SIP) and H.323. Calls can be made from the IP network to the PSTN and vice versa through the use of a gateway. The gateway translates the packets from the IP network to circuits on the PSTN and vice versa to facilitate calls between the two networks. Gateways have evolved and are now split into two entities using the master/slave architecture. The master is an intelligent Media Gateway Controller (MGC) that handles the call control and signalling. The slave is a "dumb" Media Gateway (MG) that handles the translation of the media. The current gateway control protocols in use are Megaco/H.248, MGCP and Skinny. These protocols have proved themselves on the edge of the network. Furthermore, since they communicate with the call signalling VoIP protocols as well as the PSTN, they have to be the lingua franca between the two networks. Within the VoIP network, the numbers of call signalling protocols make it difficult to communicate with each other and to create services. This research investigates the use of Gateway Control Protocols as the lowest common denominator between the call signalling protocols SIP and H.323. More specifically, it uses MGCP to investigate service creation. It also considers the use of MGCP as a protocol translator between SIP and H.323. A service was created using MGCP to allow H.323 endpoints to send Short Message Service (SMS) messages. This service was then extended with minimal effort to SIP endpoints. This service investigated MGCP’s ability to handle call control from the H.323 and SIP endpoints. An MGC was then successfully used to perform as a protocol translator between SIP and H.323.
- Full Text:
- Date Issued: 2005
- Authors: Jacobs, Ashley
- Date: 2005 , 2005-03-14
- Subjects: Communication -- Technological innovations , Digital telephone systems , Computer networks , Computer network protocols , Internet telephony
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4631 , http://hdl.handle.net/10962/d1006516 , Communication -- Technological innovations , Digital telephone systems , Computer networks , Computer network protocols , Internet telephony
- Description: Telephony used to mean using a telephone to call another telephone on the Public Switched Telephone Network (PSTN), and data networks were used purely to allow computers to communicate. However, with the advent of the Internet, telephony services have been extended to run on data networks. Telephone calls within the IP network are known as Voice over IP. These calls are carried by a number of protocols, with the most popular ones currently being Session Initiation Protocol (SIP) and H.323. Calls can be made from the IP network to the PSTN and vice versa through the use of a gateway. The gateway translates the packets from the IP network to circuits on the PSTN and vice versa to facilitate calls between the two networks. Gateways have evolved and are now split into two entities using the master/slave architecture. The master is an intelligent Media Gateway Controller (MGC) that handles the call control and signalling. The slave is a "dumb" Media Gateway (MG) that handles the translation of the media. The current gateway control protocols in use are Megaco/H.248, MGCP and Skinny. These protocols have proved themselves on the edge of the network. Furthermore, since they communicate with the call signalling VoIP protocols as well as the PSTN, they have to be the lingua franca between the two networks. Within the VoIP network, the numbers of call signalling protocols make it difficult to communicate with each other and to create services. This research investigates the use of Gateway Control Protocols as the lowest common denominator between the call signalling protocols SIP and H.323. More specifically, it uses MGCP to investigate service creation. It also considers the use of MGCP as a protocol translator between SIP and H.323. A service was created using MGCP to allow H.323 endpoints to send Short Message Service (SMS) messages. This service was then extended with minimal effort to SIP endpoints. This service investigated MGCP’s ability to handle call control from the H.323 and SIP endpoints. An MGC was then successfully used to perform as a protocol translator between SIP and H.323.
- Full Text:
- Date Issued: 2005
Investigation into the biological removal of sulphate from ethanol distillery wastewater using sulphate-reducing prokaryotes
- Authors: Smuts, Lizl
- Date: 2005
- Subjects: Sewage -- Purification -- Biological treatment , Prokaryotes , Sulfates , Distilleries -- Waste disposal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3941 , http://hdl.handle.net/10962/d1004000 , Sewage -- Purification -- Biological treatment , Prokaryotes , Sulfates , Distilleries -- Waste disposal
- Description: Ethanol production wastewater is known to be toxic, and is not easily biodegradable. It also consists of a variety of coloured components adding to the complex composition of this wastewater. Disposal of this wastewater into water courses is not recommended and yet is performed all over the world. Investigation of this wastewater found that there was a high concentration of sulphate which, in the presence of sulphate-reducing prokaryotes can cause sulphide corrosion of cement. The concentration of sulphate in the wastewater was approximately 2770 mg/L. It was also found that the wastewater pH was very low and discharge of the wastewater into the wastewater treatment works caused a negative impact on the overall quality of the final wastewater discharged to sea. It was found using FISH techniques that there were no sulphate-reducing prokaryotes present in the wastewaters but that a sulphate-reducing population existed on the sewer wall. An anaerobic contact process was designed to treat this wastewater targeting sulphate reduction to sulphide, to be converted into elemental sulphur and to increase the wastewater pH. The process did not achieve this aim and only approximately 20-30 % reduction in sulphate from the wastewater was achieved with little to no change in the pH. A 95 % reduction in sulphate concentration was needed in order to reach acceptable discharge limits. Sulphate reduction could not be carried out, even under ideal laboratory conditions. It was found that the barrier causing the digester failure was the high concentration of phenols present in the wastewater (3.3 g/L) together with the production of high concentrations of volatile fatty acids (on average 13 g acetic/L). These two components are known to cause digester failure, especially phenols, and phenols are usually only degraded by fungal species. It was concluded that the wastewater itself was not amenable to this method of biological treatment.
- Full Text:
- Date Issued: 2005
- Authors: Smuts, Lizl
- Date: 2005
- Subjects: Sewage -- Purification -- Biological treatment , Prokaryotes , Sulfates , Distilleries -- Waste disposal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3941 , http://hdl.handle.net/10962/d1004000 , Sewage -- Purification -- Biological treatment , Prokaryotes , Sulfates , Distilleries -- Waste disposal
- Description: Ethanol production wastewater is known to be toxic, and is not easily biodegradable. It also consists of a variety of coloured components adding to the complex composition of this wastewater. Disposal of this wastewater into water courses is not recommended and yet is performed all over the world. Investigation of this wastewater found that there was a high concentration of sulphate which, in the presence of sulphate-reducing prokaryotes can cause sulphide corrosion of cement. The concentration of sulphate in the wastewater was approximately 2770 mg/L. It was also found that the wastewater pH was very low and discharge of the wastewater into the wastewater treatment works caused a negative impact on the overall quality of the final wastewater discharged to sea. It was found using FISH techniques that there were no sulphate-reducing prokaryotes present in the wastewaters but that a sulphate-reducing population existed on the sewer wall. An anaerobic contact process was designed to treat this wastewater targeting sulphate reduction to sulphide, to be converted into elemental sulphur and to increase the wastewater pH. The process did not achieve this aim and only approximately 20-30 % reduction in sulphate from the wastewater was achieved with little to no change in the pH. A 95 % reduction in sulphate concentration was needed in order to reach acceptable discharge limits. Sulphate reduction could not be carried out, even under ideal laboratory conditions. It was found that the barrier causing the digester failure was the high concentration of phenols present in the wastewater (3.3 g/L) together with the production of high concentrations of volatile fatty acids (on average 13 g acetic/L). These two components are known to cause digester failure, especially phenols, and phenols are usually only degraded by fungal species. It was concluded that the wastewater itself was not amenable to this method of biological treatment.
- Full Text:
- Date Issued: 2005
Investigation of the effect of selected polypropylene fibres and ultra-fine aggregate on plastic shrinkage cracks on South African roads
- Authors: Kluyts, Grant
- Date: 2005
- Subjects: Concrete roads -- South Africa -- Design and construction , Fiber-reinforced concrete , Reinforced concrete -- Cracking , Concrete -- Expansion and contraction , Polypropylene fibers
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:9592 , http://hdl.handle.net/10948/174 , Concrete roads -- South Africa -- Design and construction , Fiber-reinforced concrete , Reinforced concrete -- Cracking , Concrete -- Expansion and contraction , Polypropylene fibers
- Description: Plastic shrinkage cracks, although not inherently structurally debilitating, expose the reinforcement in low-volume reinforced concrete roads to deleterious substances, which may reduce its effectiveness leading ultimately to structural failure. In un-reinforced low-volume concrete road these cracks appear unsightly and cause the road user an unpleasant riding experience. Many researchers believe that plastic shrinkage crack development remains a concern to the concrete industry, occurring in particularly large–area pours such as low-volume concrete roads, and therefore requires further research to understand their formation and minimization. This study reports findings on the effectiveness of oxyfluorinated polypropylene fibres to control plastic shrinkage cracks, and the effect the addition of ultra-fine material has on the formation and/or propagation of these cracks. Findings indicate that low volume dosages (2 kg/m³), of oxyfluorinated polypropylene fibre significantly reduced the formation of plastic shrinkage cracks under test conditions. Furthermore, that the addition of ultra-fine material in excess of 63 kg/m³ increased the formation and/or development of plastic shrinkage cracks.
- Full Text:
- Date Issued: 2005
- Authors: Kluyts, Grant
- Date: 2005
- Subjects: Concrete roads -- South Africa -- Design and construction , Fiber-reinforced concrete , Reinforced concrete -- Cracking , Concrete -- Expansion and contraction , Polypropylene fibers
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:9592 , http://hdl.handle.net/10948/174 , Concrete roads -- South Africa -- Design and construction , Fiber-reinforced concrete , Reinforced concrete -- Cracking , Concrete -- Expansion and contraction , Polypropylene fibers
- Description: Plastic shrinkage cracks, although not inherently structurally debilitating, expose the reinforcement in low-volume reinforced concrete roads to deleterious substances, which may reduce its effectiveness leading ultimately to structural failure. In un-reinforced low-volume concrete road these cracks appear unsightly and cause the road user an unpleasant riding experience. Many researchers believe that plastic shrinkage crack development remains a concern to the concrete industry, occurring in particularly large–area pours such as low-volume concrete roads, and therefore requires further research to understand their formation and minimization. This study reports findings on the effectiveness of oxyfluorinated polypropylene fibres to control plastic shrinkage cracks, and the effect the addition of ultra-fine material has on the formation and/or propagation of these cracks. Findings indicate that low volume dosages (2 kg/m³), of oxyfluorinated polypropylene fibre significantly reduced the formation of plastic shrinkage cracks under test conditions. Furthermore, that the addition of ultra-fine material in excess of 63 kg/m³ increased the formation and/or development of plastic shrinkage cracks.
- Full Text:
- Date Issued: 2005
Isolation and characterization of a novel thermostable and catalytically efficient laccase from Peniophora sp. strain UD4
- Authors: Jordaan, Justin
- Date: 2005
- Subjects: Enzymes Enzymes -- Industrial applications Peniophora Laccase
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3970 , http://hdl.handle.net/10962/d1004029
- Description: Enzymes are becoming an effective tool in industrial processes, from crude applications such as bioremediation to fine processes such as chirally selective biocatalysis. The ligninolytic enzymes have recently received considerable attention for industrial application due to both their broad substrate range and their ability to degrade the most recalcitrant natural polymer, lignin. This group of enzymes was therefore identified as the target group for this study. Improved enzyme properties are constantly being sought to enhance the range of applications for enzymes. Biodiversity provides a wide variety of enzymes. Several researchers have concentrated on extremophiles as their primary source of superior enzymes, consequently neglecting temperate environments in their search for these enzymes. The relatively neglected fungal biodiversity of South Africa provided an opportunity to test the hypothesis that potentially important industrial enzymes with unusual properties could be isolated from mesophilic basidiomycetous fungi. Subsequent screening of Eastern Cape biodiversity for thermostable ligninolytic enzymes from basidiomycetes resulted in the isolation of a novel laccase enzyme from a basidiomycetous species. This fungus was identified as Peniophora sp. UD4 by phylogenetic analysis of rDNA ITS sequences. Initial studies indicated a superior optimum temperature of 70°C and thermostability, indicated by no loss in activity at 60°C over nine hours. Further characterization of the laccase revealed a broader than usual substrate range through its unusual ability to oxidatively couple DMAB and MBTH. The laccase also exhibited a broad pH oxidation range for ABTS (pH 2 – 6.8), and a relatively high affinity (K_m_ = 0.0123 mM) and catalytic efficiency (63 252 mM^(-1)^s^(-1)^) for ABTS as a substrate. The laccase activity from Peniophora sp. UD4 was shown to be comprised of three isozymes with a molecular weight of 62 kDa and pI’s of 6.33, 6.45 and 6.50. Investigation of the nutrient and physical factors affecting ligninolytic enzyme production and growth of Peniophora sp. UD4 indicated that the wild-type organism was unsuitable for large scale production of the thermostable laccase due to the low levels of laccase production. The thermostable laccase was applied to defouling of ultrafiltration membranes, bioremediation of industrial waste streams, biocatalysis, and biosensor technology as potential applications. Application of the Peniophora sp. UD4 laccase to defouling of membranes used for ultrafiltration of brown water showed large flux recoveries of 31, 21 and 21% after the first three defouling recycles respectively, compared to 3% for the control without immobilized enzyme. The novel laccase showed potential for the bioremediation of industrial waste streams, the most successful being that of bleach plant effluent, where a reduction of 66% of the phenolic load was achieved. Application of the novel laccase to biocatalytic oxidation of ferulic acid and (±)-α-pinene showed higher product yield as compared to oxidation of these compounds by Trametes versicolor laccase in mediated and non-mediated systems. The major products of (±)-α-pinene oxidation were identified as verbenol and trans-sorberol. The Peniophora sp. UD4 laccase was successfully applied to biosensor technology, which benchmarked significantly better than Trametes versicolor laccase for the detection of 4-chlorophenol. The biosensor developed with laccase from UD4 by covalent binding to a glassy carbon electrode exhibited the best combination of sensitivity and stability. This thesis shows that a laccase with superior properties was obtained from a mesophilic South African basidiomycete. The catalytic properties displayed by the novel laccase from Peniophora sp. UD4 all contribute to the increased industrial applicability of laccases, and may be the most industrially feasible enzyme of its class isolated to date.
- Full Text:
- Date Issued: 2005
- Authors: Jordaan, Justin
- Date: 2005
- Subjects: Enzymes Enzymes -- Industrial applications Peniophora Laccase
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3970 , http://hdl.handle.net/10962/d1004029
- Description: Enzymes are becoming an effective tool in industrial processes, from crude applications such as bioremediation to fine processes such as chirally selective biocatalysis. The ligninolytic enzymes have recently received considerable attention for industrial application due to both their broad substrate range and their ability to degrade the most recalcitrant natural polymer, lignin. This group of enzymes was therefore identified as the target group for this study. Improved enzyme properties are constantly being sought to enhance the range of applications for enzymes. Biodiversity provides a wide variety of enzymes. Several researchers have concentrated on extremophiles as their primary source of superior enzymes, consequently neglecting temperate environments in their search for these enzymes. The relatively neglected fungal biodiversity of South Africa provided an opportunity to test the hypothesis that potentially important industrial enzymes with unusual properties could be isolated from mesophilic basidiomycetous fungi. Subsequent screening of Eastern Cape biodiversity for thermostable ligninolytic enzymes from basidiomycetes resulted in the isolation of a novel laccase enzyme from a basidiomycetous species. This fungus was identified as Peniophora sp. UD4 by phylogenetic analysis of rDNA ITS sequences. Initial studies indicated a superior optimum temperature of 70°C and thermostability, indicated by no loss in activity at 60°C over nine hours. Further characterization of the laccase revealed a broader than usual substrate range through its unusual ability to oxidatively couple DMAB and MBTH. The laccase also exhibited a broad pH oxidation range for ABTS (pH 2 – 6.8), and a relatively high affinity (K_m_ = 0.0123 mM) and catalytic efficiency (63 252 mM^(-1)^s^(-1)^) for ABTS as a substrate. The laccase activity from Peniophora sp. UD4 was shown to be comprised of three isozymes with a molecular weight of 62 kDa and pI’s of 6.33, 6.45 and 6.50. Investigation of the nutrient and physical factors affecting ligninolytic enzyme production and growth of Peniophora sp. UD4 indicated that the wild-type organism was unsuitable for large scale production of the thermostable laccase due to the low levels of laccase production. The thermostable laccase was applied to defouling of ultrafiltration membranes, bioremediation of industrial waste streams, biocatalysis, and biosensor technology as potential applications. Application of the Peniophora sp. UD4 laccase to defouling of membranes used for ultrafiltration of brown water showed large flux recoveries of 31, 21 and 21% after the first three defouling recycles respectively, compared to 3% for the control without immobilized enzyme. The novel laccase showed potential for the bioremediation of industrial waste streams, the most successful being that of bleach plant effluent, where a reduction of 66% of the phenolic load was achieved. Application of the novel laccase to biocatalytic oxidation of ferulic acid and (±)-α-pinene showed higher product yield as compared to oxidation of these compounds by Trametes versicolor laccase in mediated and non-mediated systems. The major products of (±)-α-pinene oxidation were identified as verbenol and trans-sorberol. The Peniophora sp. UD4 laccase was successfully applied to biosensor technology, which benchmarked significantly better than Trametes versicolor laccase for the detection of 4-chlorophenol. The biosensor developed with laccase from UD4 by covalent binding to a glassy carbon electrode exhibited the best combination of sensitivity and stability. This thesis shows that a laccase with superior properties was obtained from a mesophilic South African basidiomycete. The catalytic properties displayed by the novel laccase from Peniophora sp. UD4 all contribute to the increased industrial applicability of laccases, and may be the most industrially feasible enzyme of its class isolated to date.
- Full Text:
- Date Issued: 2005
Isolation, purification and characterization of inulin and fructooligosaccharides from chicorium intybus and inulinase from aspergillus niger
- Mavumengwana, Vuyo Bhongelethu
- Authors: Mavumengwana, Vuyo Bhongelethu
- Date: 2005
- Subjects: Aspergillus , Inulin , Chicory -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3954 , http://hdl.handle.net/10962/d1004013 , Aspergillus , Inulin , Chicory -- South Africa
- Description: Inulin is a non-digestible carbohydrate fructan polymer consisting mainly of β (1→2) fructosyl fructose links. Enzymatic hydrolysis of inulin by inulinase results in the production of low D.P (degree of polymerization) oligosaccharides also called fructooligosaccharides(FOS). Isolation of inulin from chicory root (Chicorium intybus) was achieved by first, extraction using deionized water (600C), followed by carbonation (0.1 M Ca(OH)2 and CO2 gas). This was filtered in order to remove the non sugars, thereafter, treated successfully with polyamide 6 powder. A cation exchanger and an anion exchanger were used to further exclude other components such as tannins and pigments. The extracted inulin was quantified using the Somogyi-Nelson colourimetric assay. Chicory root (207 g, 30 % being water) yielded 30 g of the raw extract. A 100 mg of the raw extract was assayed and found to contain 11 % yield of inulin which was 80.2 % in purity and 4 % free fructose. Analysis of the crude and purified inulin extracts on the MALDI TOF spectrometry showed the samples to have a DP of 2 to 22 and 2 to 27 respectively. Maximum inulinase production from Aspergillus niger grown on inulin was observed after 60 hours. The enzyme activity was found to be 1.168 U/ml with a temperature and pH optimum of 30 °C and 7.7 respectively. The enzyme proved to be unstable as it progressively lost its total activity during attempts at purification.
- Full Text:
- Date Issued: 2005
- Authors: Mavumengwana, Vuyo Bhongelethu
- Date: 2005
- Subjects: Aspergillus , Inulin , Chicory -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3954 , http://hdl.handle.net/10962/d1004013 , Aspergillus , Inulin , Chicory -- South Africa
- Description: Inulin is a non-digestible carbohydrate fructan polymer consisting mainly of β (1→2) fructosyl fructose links. Enzymatic hydrolysis of inulin by inulinase results in the production of low D.P (degree of polymerization) oligosaccharides also called fructooligosaccharides(FOS). Isolation of inulin from chicory root (Chicorium intybus) was achieved by first, extraction using deionized water (600C), followed by carbonation (0.1 M Ca(OH)2 and CO2 gas). This was filtered in order to remove the non sugars, thereafter, treated successfully with polyamide 6 powder. A cation exchanger and an anion exchanger were used to further exclude other components such as tannins and pigments. The extracted inulin was quantified using the Somogyi-Nelson colourimetric assay. Chicory root (207 g, 30 % being water) yielded 30 g of the raw extract. A 100 mg of the raw extract was assayed and found to contain 11 % yield of inulin which was 80.2 % in purity and 4 % free fructose. Analysis of the crude and purified inulin extracts on the MALDI TOF spectrometry showed the samples to have a DP of 2 to 22 and 2 to 27 respectively. Maximum inulinase production from Aspergillus niger grown on inulin was observed after 60 hours. The enzyme activity was found to be 1.168 U/ml with a temperature and pH optimum of 30 °C and 7.7 respectively. The enzyme proved to be unstable as it progressively lost its total activity during attempts at purification.
- Full Text:
- Date Issued: 2005
Knowledge levels of school learners before and after a life skills program on rape and child abuse
- Authors: Britz, Cecelia Adonia
- Date: 2005
- Subjects: Rape -- Prevention , Child abuse -- Prevention , School children -- Life skills assessment -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:11017 , http://hdl.handle.net/10948/360 , Rape -- Prevention , Child abuse -- Prevention , School children -- Life skills assessment -- South Africa -- Port Elizabeth
- Description: Due to the early age at which children are exposed to rape and child abuse, preventative programs should be implemented as early as possible. Schools provide ample opportunity to reach learners of all ages. Educators have regular contact with learners and have a key role to play in the implementation of comprehensive health and education life skills programs. Non-Governmental Organisations (NGO) can link up with schools to combat abuse that affects children in South African communities. The Ubuntu Education Fund requested the Health and Development Research Institute (HDRI) of the University of Port Elizabeth to assist with the evaluation of the Mpilo-Lwazi life skills program for grade 6 to 9 learners at 5 primary and 5 secondary schools in the Nelson Mandela Metropole. The schools were selected by non-probability convenience sampling and the learners via simple random sampling. The life skills program addressed issues of HIV/AIDS, STI and rape and child abuse and the requested evaluation encompassed both the quantitative pretest-posttest assessment of knowledge plus a qualitative focus group assessment of perception of the content and presentation of the life skills program. A multiple pretest-post-test quasi-experimental research design was used. This study focused on the quantitative aspect of rape and child abuse and aimed to describe learners’ base line knowledge before receiving education in rape and child abuse life skills programs and acquired knowledge after the program had been implemented. Descriptive statistics were employed to describe the pre and post test information and the Hotelling’s T2 was used to identify variation in profiles. Posthoc t-tests established significant differences between grades. Structured questionnaires were used to achieve the aims of the research. Results of both the quantitative and qualitative findings were collated to be presented to the Ubuntu Education Fund. The results of the study were as follows: ix The results indicated that the overall level of knowledge regarding Rape and Child Abuse among the sample of grade six to nine learners was average. A small increase in knowledge was identified in the post-test. The area most successful for knowledge increase was the section relating to general information on the victims of Rape and Child Abuse. An area where knowledge actually decreased was that on reporting the rape or abuse. Knowledge of rape and child abuse alone is not sufficient to bring about change in behaviour. Changes in beliefs, such as increased awareness that rape and child abuse are prevalent in families and communities, and attitude change are necessary to facilitate the adoption of health-promoting behaviour. Future education efforts need to introduce health educators into the Rape and Child Abuse life skills program at schools in educating the learners. The format of teaching should also take into account the preferred method of presentation indicated by the learners as this would facilitate optimal intake of information.
- Full Text:
- Date Issued: 2005
- Authors: Britz, Cecelia Adonia
- Date: 2005
- Subjects: Rape -- Prevention , Child abuse -- Prevention , School children -- Life skills assessment -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:11017 , http://hdl.handle.net/10948/360 , Rape -- Prevention , Child abuse -- Prevention , School children -- Life skills assessment -- South Africa -- Port Elizabeth
- Description: Due to the early age at which children are exposed to rape and child abuse, preventative programs should be implemented as early as possible. Schools provide ample opportunity to reach learners of all ages. Educators have regular contact with learners and have a key role to play in the implementation of comprehensive health and education life skills programs. Non-Governmental Organisations (NGO) can link up with schools to combat abuse that affects children in South African communities. The Ubuntu Education Fund requested the Health and Development Research Institute (HDRI) of the University of Port Elizabeth to assist with the evaluation of the Mpilo-Lwazi life skills program for grade 6 to 9 learners at 5 primary and 5 secondary schools in the Nelson Mandela Metropole. The schools were selected by non-probability convenience sampling and the learners via simple random sampling. The life skills program addressed issues of HIV/AIDS, STI and rape and child abuse and the requested evaluation encompassed both the quantitative pretest-posttest assessment of knowledge plus a qualitative focus group assessment of perception of the content and presentation of the life skills program. A multiple pretest-post-test quasi-experimental research design was used. This study focused on the quantitative aspect of rape and child abuse and aimed to describe learners’ base line knowledge before receiving education in rape and child abuse life skills programs and acquired knowledge after the program had been implemented. Descriptive statistics were employed to describe the pre and post test information and the Hotelling’s T2 was used to identify variation in profiles. Posthoc t-tests established significant differences between grades. Structured questionnaires were used to achieve the aims of the research. Results of both the quantitative and qualitative findings were collated to be presented to the Ubuntu Education Fund. The results of the study were as follows: ix The results indicated that the overall level of knowledge regarding Rape and Child Abuse among the sample of grade six to nine learners was average. A small increase in knowledge was identified in the post-test. The area most successful for knowledge increase was the section relating to general information on the victims of Rape and Child Abuse. An area where knowledge actually decreased was that on reporting the rape or abuse. Knowledge of rape and child abuse alone is not sufficient to bring about change in behaviour. Changes in beliefs, such as increased awareness that rape and child abuse are prevalent in families and communities, and attitude change are necessary to facilitate the adoption of health-promoting behaviour. Future education efforts need to introduce health educators into the Rape and Child Abuse life skills program at schools in educating the learners. The format of teaching should also take into account the preferred method of presentation indicated by the learners as this would facilitate optimal intake of information.
- Full Text:
- Date Issued: 2005
Ligand isotope vibrational spectroscopic and DFT studies of Pt(II) and Cu(I) complexes
- Authors: Medina, Gerardo Juan
- Date: 2005
- Subjects: Ligands Spectrum analysis Vibrational spectra Infrared spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4324 , http://hdl.handle.net/10962/d1004982
- Description: Ligand-isotope labelling studies were performed on Zeise’s salt derivatives with pyridine N-oxide and quinoline N-oxide, their perdeuterated and O-18 isotopomers, C₂D₄ and ¹³CO, and the results of the vibrational analyses are reported. The isotopomers are modelled utilizing DFT calculations at the B3LYP level with the 6-31 G** basis set, and a pseudopotential level for the Pt atom. The calculated and observed structure and vibrational spectra correlate well. The crystal structures of [Pt(C₂2H₄)(pyO)Cl₂] and [Pt(CO)(quinO)Br₂] are reported. The frequency for the νPt-O vibration, ambiguously assigned in the literature, is here assigned unequivocally at 400 cm⁻¹. Previously observed, but inadequately described phenomena are addressed: the νN-O vibration in substituted quinoline N-oxides has been assigned previously at significantly different frequencies, depending on the nature of the substituent. This suggests that there is no specific mid-ir band associated with a high N-O character. A suitable explanation is presented for this phenomenon, showing that in low symmetry systems (eg. quinO) the N-O stretch is dispersed among several modes, whereas in high symmetry systems (eg. pyO) only a few limited modes have a high N-O character. A theoretical study of Cu(I) carbonyl compounds with macrocyclic ligands is presented. Local and global HSAB parameters applied to the donor and Cu atoms are used to explain the observed reactivities and the available spectroscopic data. Extended to [Cu(CO){H₂N(CH₂)[subscript n]NH(CH₂)[subscript m] NH₂}] BPh₄ (where n = 2, m = 2, 3 and n =3, m = 3, 4) and their -d₅ and ¹³CO isotopomers, subtle differences obtained experimentally for the CO stretching frequency in this series have been reproduced in the DFT calculations at the B3LYP level, using the 6-31 G* and 6-31 G** basis sets. Several properties (ligand pK[subscript a] values, νCO frequencies, etc.) correlate with some HSAB descriptors. Vibrational analyses are presented of Cu(I) carbonyl Schiff-base derivatives of N-Benzylidene-N’-[2-(benzyilidene-amino)-ethyl]-ethane-1,2-diamine, {2,2N3(C₆H₄R)₂}, and their -d₅ and ¹³CO isotopomers. The crystal structure of [Cu(CO){2,2N3(C₆H₅)₂}]BPh₄ is reported. From geometry optimizations and the HSAB descriptors, spectroscopic trends ([n]Cu-N and [nu]CO) are related to calculated global hardness and the Hammett substituent parameters, and are discussed in terms of σ-donation and π-backbonding of Cu- CO.
- Full Text:
- Date Issued: 2005
- Authors: Medina, Gerardo Juan
- Date: 2005
- Subjects: Ligands Spectrum analysis Vibrational spectra Infrared spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4324 , http://hdl.handle.net/10962/d1004982
- Description: Ligand-isotope labelling studies were performed on Zeise’s salt derivatives with pyridine N-oxide and quinoline N-oxide, their perdeuterated and O-18 isotopomers, C₂D₄ and ¹³CO, and the results of the vibrational analyses are reported. The isotopomers are modelled utilizing DFT calculations at the B3LYP level with the 6-31 G** basis set, and a pseudopotential level for the Pt atom. The calculated and observed structure and vibrational spectra correlate well. The crystal structures of [Pt(C₂2H₄)(pyO)Cl₂] and [Pt(CO)(quinO)Br₂] are reported. The frequency for the νPt-O vibration, ambiguously assigned in the literature, is here assigned unequivocally at 400 cm⁻¹. Previously observed, but inadequately described phenomena are addressed: the νN-O vibration in substituted quinoline N-oxides has been assigned previously at significantly different frequencies, depending on the nature of the substituent. This suggests that there is no specific mid-ir band associated with a high N-O character. A suitable explanation is presented for this phenomenon, showing that in low symmetry systems (eg. quinO) the N-O stretch is dispersed among several modes, whereas in high symmetry systems (eg. pyO) only a few limited modes have a high N-O character. A theoretical study of Cu(I) carbonyl compounds with macrocyclic ligands is presented. Local and global HSAB parameters applied to the donor and Cu atoms are used to explain the observed reactivities and the available spectroscopic data. Extended to [Cu(CO){H₂N(CH₂)[subscript n]NH(CH₂)[subscript m] NH₂}] BPh₄ (where n = 2, m = 2, 3 and n =3, m = 3, 4) and their -d₅ and ¹³CO isotopomers, subtle differences obtained experimentally for the CO stretching frequency in this series have been reproduced in the DFT calculations at the B3LYP level, using the 6-31 G* and 6-31 G** basis sets. Several properties (ligand pK[subscript a] values, νCO frequencies, etc.) correlate with some HSAB descriptors. Vibrational analyses are presented of Cu(I) carbonyl Schiff-base derivatives of N-Benzylidene-N’-[2-(benzyilidene-amino)-ethyl]-ethane-1,2-diamine, {2,2N3(C₆H₄R)₂}, and their -d₅ and ¹³CO isotopomers. The crystal structure of [Cu(CO){2,2N3(C₆H₅)₂}]BPh₄ is reported. From geometry optimizations and the HSAB descriptors, spectroscopic trends ([n]Cu-N and [nu]CO) are related to calculated global hardness and the Hammett substituent parameters, and are discussed in terms of σ-donation and π-backbonding of Cu- CO.
- Full Text:
- Date Issued: 2005
Making meaning, making a home: students watching Generations
- Authors: O'Shea, Catherine Mary
- Date: 2005
- Subjects: Generations (Television program) , Students, Black -- South Africa -- Attitudes , Television soap operas -- South Africa , Cross-cultural studies -- South Africa
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3479 , http://hdl.handle.net/10962/d1002934 , Generations (Television program) , Students, Black -- South Africa -- Attitudes , Television soap operas -- South Africa , Cross-cultural studies -- South Africa
- Description: This thesis is a reception analysis using qualitative interviews to investigate black students' watching of a South African soap opera, Generations, taking into account the context of a largely white South African university campus. The findings of this study are that students find pleasure in talking about Generations and hold seemingly contradictory views on whether it is 'realistic' or not. The analysis concludes that watching Generations does serve to affirm these students' black identity, since there is a particular need to do so on a campus where black students witness and experience racial discrimination.
- Full Text:
- Date Issued: 2005
- Authors: O'Shea, Catherine Mary
- Date: 2005
- Subjects: Generations (Television program) , Students, Black -- South Africa -- Attitudes , Television soap operas -- South Africa , Cross-cultural studies -- South Africa
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3479 , http://hdl.handle.net/10962/d1002934 , Generations (Television program) , Students, Black -- South Africa -- Attitudes , Television soap operas -- South Africa , Cross-cultural studies -- South Africa
- Description: This thesis is a reception analysis using qualitative interviews to investigate black students' watching of a South African soap opera, Generations, taking into account the context of a largely white South African university campus. The findings of this study are that students find pleasure in talking about Generations and hold seemingly contradictory views on whether it is 'realistic' or not. The analysis concludes that watching Generations does serve to affirm these students' black identity, since there is a particular need to do so on a campus where black students witness and experience racial discrimination.
- Full Text:
- Date Issued: 2005
Marine biotechnology : evaluation and development of methods for the discovery of natural products from fungi
- Authors: Pather, Simisha
- Date: 2005 , 2013-06-18
- Subjects: Marine biotechnology , Marine fungi -- South Africa , Natural products -- South Africa , Marine plants -- South Africa , Marine metabolites -- South Africa , Cancer -- Treatment , DNA
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3839 , http://hdl.handle.net/10962/d1007652 , Marine biotechnology , Marine fungi -- South Africa , Natural products -- South Africa , Marine plants -- South Africa , Marine metabolites -- South Africa , Cancer -- Treatment , DNA
- Description: One of the major impediments in the development of marine natural products is the provision of biologically active natural products in sufficient quantity for complete pharmacological evaluation, clinical trials and eventual commercial production. Marine microorganisms show great promise in providing a renewable source of biologically active natural products. The main aim of this study was to develop and evaluate methods for the isolation, identification and cultivation of marine fungi from the South African marine environment for the production of biologically active secondary metabolites. Twenty-four species of fungi were isolated from marine algae collected from the intertidal zone near Port Alfred, South Africa. The fungi were cultivated in small-scale under static and agitated conditions and their crude intra- and extracellular organic extracts were screened by ¹H NMR and a series of bioassays. Using this as a basis, one isolate was selected for further study. By analyses of the lTS1 region of the ribosomal DNA, the fungal isolate was identified as a marine-derived isolate of Eurotium rubrum (Aspergillus ruber). Although E. rubrum has been isolated from the marine environment, no investigations have been undertaken to determine the adaptation of these isolates to the marine environment. In order to optimise productivity, creativity and incubation time, the fungus was cultivated in small-scale using a variety of carbon (glucose, fructose, lactose, sucrose, marmitol and maltose) and nitrogen sources (ammonium tartrate, urea, peptone and yeast extract). An HPLC-DAD method was developed to assess the metabolic creativity and productivity under different fermentation conditions. Distinctive variations in the range and yield of metabolites produced as well as morphology and growth time were observed. The crude extracts from all fermentations were combined and six known compounds were isolated by reversed-phase chromatography and their structures elucidated by spectroscopic techniques. The known compounds were fIavoglaucin, aspergin, isodihydroauroglaucin, isotetrahydroauroglaucin, neoechinuline A and physcion. Neoechinuline A, isodihydroauroglaucin and isotetrahydroauroglaucin showed activity against oesophageal and cervical cancer cell lines.
- Full Text:
- Date Issued: 2005
- Authors: Pather, Simisha
- Date: 2005 , 2013-06-18
- Subjects: Marine biotechnology , Marine fungi -- South Africa , Natural products -- South Africa , Marine plants -- South Africa , Marine metabolites -- South Africa , Cancer -- Treatment , DNA
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3839 , http://hdl.handle.net/10962/d1007652 , Marine biotechnology , Marine fungi -- South Africa , Natural products -- South Africa , Marine plants -- South Africa , Marine metabolites -- South Africa , Cancer -- Treatment , DNA
- Description: One of the major impediments in the development of marine natural products is the provision of biologically active natural products in sufficient quantity for complete pharmacological evaluation, clinical trials and eventual commercial production. Marine microorganisms show great promise in providing a renewable source of biologically active natural products. The main aim of this study was to develop and evaluate methods for the isolation, identification and cultivation of marine fungi from the South African marine environment for the production of biologically active secondary metabolites. Twenty-four species of fungi were isolated from marine algae collected from the intertidal zone near Port Alfred, South Africa. The fungi were cultivated in small-scale under static and agitated conditions and their crude intra- and extracellular organic extracts were screened by ¹H NMR and a series of bioassays. Using this as a basis, one isolate was selected for further study. By analyses of the lTS1 region of the ribosomal DNA, the fungal isolate was identified as a marine-derived isolate of Eurotium rubrum (Aspergillus ruber). Although E. rubrum has been isolated from the marine environment, no investigations have been undertaken to determine the adaptation of these isolates to the marine environment. In order to optimise productivity, creativity and incubation time, the fungus was cultivated in small-scale using a variety of carbon (glucose, fructose, lactose, sucrose, marmitol and maltose) and nitrogen sources (ammonium tartrate, urea, peptone and yeast extract). An HPLC-DAD method was developed to assess the metabolic creativity and productivity under different fermentation conditions. Distinctive variations in the range and yield of metabolites produced as well as morphology and growth time were observed. The crude extracts from all fermentations were combined and six known compounds were isolated by reversed-phase chromatography and their structures elucidated by spectroscopic techniques. The known compounds were fIavoglaucin, aspergin, isodihydroauroglaucin, isotetrahydroauroglaucin, neoechinuline A and physcion. Neoechinuline A, isodihydroauroglaucin and isotetrahydroauroglaucin showed activity against oesophageal and cervical cancer cell lines.
- Full Text:
- Date Issued: 2005
Material characterisation of laser formed dual phase steel components
- Authors: Els-Botes, Annelize
- Date: 2005
- Subjects: Steel -- Fatigue , Bending , Lasers , Sheet-steel -- Effect of lasers on
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:9609 , http://hdl.handle.net/10948/176 , Steel -- Fatigue , Bending , Lasers , Sheet-steel -- Effect of lasers on
- Description: The nature and scope of this thesis can be divided into four categories: • FORMING PARAMETERS • Identification of various laser forming parameters in order to produce specimens of similar dimension (radius of curvature). • TEMPERATURE AND MICROSTRUCTURE • To study the effect of maximum temperature reached during the forming operation on the microstructure of the various specimens. • FATIGUE LIFE • Compare the fatigue life of the specimens produced by various laser parameters to that of the original material, and also the fatigue life of mechanical formed specimens. • RESIDUAL STRESS PROFILE Determine if the laser forming process induces detrimental residual stress magnitudes in the specimens. The main objective of this thesis was to gain an understanding of the way in which laser forming affects the fatigue performance and residual stress magnitude / distribution of dual phase steel. Although lasers have been used successfully in various manufacturing processes (welding, cutting, marking, etc.), little information is available on the influence of laser forming on many automotive alloys such as dual phase steel. The first part of the work involved a literature review of the process and factors affecting the laser forming process. It became clear from the literature overview that laser forming of sheet material thicker than 1mm is complex in nature. The variables that can influence the process are complicated and their interaction with each other is not easily controlled. The main parameters that were thus controlled in this study are as follows: • Laser power (P) • Laser head travel speed (v) • Laser beam size (mm) The chapters that follow the literature review, deals with the laser forming process of dual phase steel and the production of fatigue specimens using various laser parameters. It was found that the following laser parameters resulted in specimens with approximately the same radius of curvature: Laser power KW Beam diameter mm Interval spacing % Overlap Scanning velocity m/min Line Energy J/m 5 20 10 50 2,5 2000 3,1 14 10,5 25 2 1550 1,5 7,5 7,5 0 1,2 1250 From the results obtained from fatigue testing specimens produced with the above settings, it is clear that the laser forming process has the potential to be employed as a production stage in the manufacture of wheel centre discs while maintaining adequate fatigue strength. Large beam diameters which cause heat penetration through the thickness of the specimen and hence microstructure breakdown should be avoided, since it was shown that these specimens exhibited impaired mechanical properties than those produced with a smaller laser beam diameter. The microstructural changes observed during the forming process needs to be considered since the mechanical properties of the material changes with a change in microstructure. A dramatic change in microstructure was observed; therefore it is of crucial importance that microstructural evaluation plays an important part in deciding optimum laser parameters for the forming process of ferrous alloys. During residual stress analysis, trends were observed between measurements taken at the same location of the samples; regardless whether measurements were taken on the laser irradiated side or the reverse side of the specimen. The only difference was the magnitude of the relieved residual stress. In most cases the obtained relieved residual stress was much smaller in magnitude than that of the original plate (in the bulk of the material). The surface indicated a slight tensile residual stress for most samples evaluated. A good correlation in distribution profile was obtained between microhardness and relieved residual stress distribution at the ‘middle of sample’ location. This indicates that an increase in hardness indicates an increase in residual stress magnitude for the laser formed specimens. In conclusion, this research has proved that it is possible to deform metal plate of a 3,5mm thickness with a CO2 laser system. The research also established the effect of process parameters on the final product’s shape/bend angle and characterised the effect of the laser forming process on the material’s mechanical properties and structural integrity.
- Full Text:
- Date Issued: 2005
- Authors: Els-Botes, Annelize
- Date: 2005
- Subjects: Steel -- Fatigue , Bending , Lasers , Sheet-steel -- Effect of lasers on
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:9609 , http://hdl.handle.net/10948/176 , Steel -- Fatigue , Bending , Lasers , Sheet-steel -- Effect of lasers on
- Description: The nature and scope of this thesis can be divided into four categories: • FORMING PARAMETERS • Identification of various laser forming parameters in order to produce specimens of similar dimension (radius of curvature). • TEMPERATURE AND MICROSTRUCTURE • To study the effect of maximum temperature reached during the forming operation on the microstructure of the various specimens. • FATIGUE LIFE • Compare the fatigue life of the specimens produced by various laser parameters to that of the original material, and also the fatigue life of mechanical formed specimens. • RESIDUAL STRESS PROFILE Determine if the laser forming process induces detrimental residual stress magnitudes in the specimens. The main objective of this thesis was to gain an understanding of the way in which laser forming affects the fatigue performance and residual stress magnitude / distribution of dual phase steel. Although lasers have been used successfully in various manufacturing processes (welding, cutting, marking, etc.), little information is available on the influence of laser forming on many automotive alloys such as dual phase steel. The first part of the work involved a literature review of the process and factors affecting the laser forming process. It became clear from the literature overview that laser forming of sheet material thicker than 1mm is complex in nature. The variables that can influence the process are complicated and their interaction with each other is not easily controlled. The main parameters that were thus controlled in this study are as follows: • Laser power (P) • Laser head travel speed (v) • Laser beam size (mm) The chapters that follow the literature review, deals with the laser forming process of dual phase steel and the production of fatigue specimens using various laser parameters. It was found that the following laser parameters resulted in specimens with approximately the same radius of curvature: Laser power KW Beam diameter mm Interval spacing % Overlap Scanning velocity m/min Line Energy J/m 5 20 10 50 2,5 2000 3,1 14 10,5 25 2 1550 1,5 7,5 7,5 0 1,2 1250 From the results obtained from fatigue testing specimens produced with the above settings, it is clear that the laser forming process has the potential to be employed as a production stage in the manufacture of wheel centre discs while maintaining adequate fatigue strength. Large beam diameters which cause heat penetration through the thickness of the specimen and hence microstructure breakdown should be avoided, since it was shown that these specimens exhibited impaired mechanical properties than those produced with a smaller laser beam diameter. The microstructural changes observed during the forming process needs to be considered since the mechanical properties of the material changes with a change in microstructure. A dramatic change in microstructure was observed; therefore it is of crucial importance that microstructural evaluation plays an important part in deciding optimum laser parameters for the forming process of ferrous alloys. During residual stress analysis, trends were observed between measurements taken at the same location of the samples; regardless whether measurements were taken on the laser irradiated side or the reverse side of the specimen. The only difference was the magnitude of the relieved residual stress. In most cases the obtained relieved residual stress was much smaller in magnitude than that of the original plate (in the bulk of the material). The surface indicated a slight tensile residual stress for most samples evaluated. A good correlation in distribution profile was obtained between microhardness and relieved residual stress distribution at the ‘middle of sample’ location. This indicates that an increase in hardness indicates an increase in residual stress magnitude for the laser formed specimens. In conclusion, this research has proved that it is possible to deform metal plate of a 3,5mm thickness with a CO2 laser system. The research also established the effect of process parameters on the final product’s shape/bend angle and characterised the effect of the laser forming process on the material’s mechanical properties and structural integrity.
- Full Text:
- Date Issued: 2005
Metalorganic vapour phase epitaxial growth and characterisation of Sb-based semiconductors
- Authors: Vankova, Viera
- Date: 2005
- Subjects: Compound semiconductors , Epitaxy , Organometallic compounds , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10548 , http://hdl.handle.net/10948/d1019678
- Description: This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.
- Full Text:
- Date Issued: 2005
- Authors: Vankova, Viera
- Date: 2005
- Subjects: Compound semiconductors , Epitaxy , Organometallic compounds , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10548 , http://hdl.handle.net/10948/d1019678
- Description: This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.
- Full Text:
- Date Issued: 2005