Advances in platinum-amine chemotherapeutic agents : their chemistry and applicationc
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
An investigation into the use of guidelines and patterns in the interaction design process
- Authors: Cowley, Niel Lester Orr
- Date: 2009
- Subjects: Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10466 , http://hdl.handle.net/10948/1062 , Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Description: Design guidelines are used in interaction design (IxD) for physical design and for evaluating the usability of designs and interactive products. Guidelines are widely used for physical design and evaluation, but have a number of problems. IxD patterns have been proposed as an alternative to guidelines, as they are claimed to have several advantages over guidelines. A small number of empirical studies provide evidence that patterns are beneficial when used in IxD. Additional research on the usefulness of IxD patterns is required. The primary research question investigated in this thesis was thus: How useful are IxD patterns as physical design and evaluation aids in IxD, as compared to design guidelines? The role of guidelines and patterns as design and evaluation aids in IxD was investigated and a comparison of guidelines and patterns, based on a set of guideline and pattern properties, was conducted. The concept of pattern and guideline usefulness was explored and a research agenda for guidelines and patterns was identified, together with a set of research questions for an empirical study. The empirical study of the use of patterns for evaluation, redesign and new design, as compared to guidelines, was conducted at the Nelson Mandela Metropolitan University in 2004. The participants were a purposive sample of post-graduate Computing students, who were regarded as novice interaction designers. Two equivalent groups were formed, one that used patterns and one that used guidelines. Patterns were found to be as useful as guidelines when used as evaluation aids. Guidelines and patterns were identified as effective tools for identifying and explaining usability issues and design features. Best-effort matched sets of guidelines and patterns produced substantially different result sets when used to identify issues and features, with fairly low overlap. A substantial evaluator effect was observed for the use of guidelines and patterns for evaluation, and the results obtained were similar to those obtained by Molich et al. in their Comparative Usability Evaluation (CUE) studies. There was no statistically significant difference between the effectiveness of guidelines and patterns for evaluation. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for evaluation. Guidelines and patterns were found to be used in similar ways for evaluation. Patterns were found to be more effective than guidelines for redesign. Patterns were found to be as useful as guidelines when used for new design. There was no statistically significant difference between the effectiveness of guidelines and patterns for new design. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for redesign and new design. Guidelines and patterns were found to be used in similar ways for design. There was no statistically significant difference between the perceived usefulness of the format, content, ease of learning, and usefulness as personal and shared design languages, of guidelines and patterns. Both participant groups were equally agreeable to using guidelines and patterns in the future. The perceived usefulness of pattern collections was found to depend on the usability of the collection interface and the content quality of the patterns. The results of the empirical study thus provided empirical evidence that patterns were as useful as guidelines for evaluation and new design, and were perceived as positively as guidelines were. Patterns were found to be superior to guidelines for redesign. Patterns can therefore be used with a measure of confidence as early stage design aids for physical design and evaluation in the future. In addition to these findings, a number of opportunities for further research were identified.
- Full Text:
- Date Issued: 2009
- Authors: Cowley, Niel Lester Orr
- Date: 2009
- Subjects: Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10466 , http://hdl.handle.net/10948/1062 , Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Description: Design guidelines are used in interaction design (IxD) for physical design and for evaluating the usability of designs and interactive products. Guidelines are widely used for physical design and evaluation, but have a number of problems. IxD patterns have been proposed as an alternative to guidelines, as they are claimed to have several advantages over guidelines. A small number of empirical studies provide evidence that patterns are beneficial when used in IxD. Additional research on the usefulness of IxD patterns is required. The primary research question investigated in this thesis was thus: How useful are IxD patterns as physical design and evaluation aids in IxD, as compared to design guidelines? The role of guidelines and patterns as design and evaluation aids in IxD was investigated and a comparison of guidelines and patterns, based on a set of guideline and pattern properties, was conducted. The concept of pattern and guideline usefulness was explored and a research agenda for guidelines and patterns was identified, together with a set of research questions for an empirical study. The empirical study of the use of patterns for evaluation, redesign and new design, as compared to guidelines, was conducted at the Nelson Mandela Metropolitan University in 2004. The participants were a purposive sample of post-graduate Computing students, who were regarded as novice interaction designers. Two equivalent groups were formed, one that used patterns and one that used guidelines. Patterns were found to be as useful as guidelines when used as evaluation aids. Guidelines and patterns were identified as effective tools for identifying and explaining usability issues and design features. Best-effort matched sets of guidelines and patterns produced substantially different result sets when used to identify issues and features, with fairly low overlap. A substantial evaluator effect was observed for the use of guidelines and patterns for evaluation, and the results obtained were similar to those obtained by Molich et al. in their Comparative Usability Evaluation (CUE) studies. There was no statistically significant difference between the effectiveness of guidelines and patterns for evaluation. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for evaluation. Guidelines and patterns were found to be used in similar ways for evaluation. Patterns were found to be more effective than guidelines for redesign. Patterns were found to be as useful as guidelines when used for new design. There was no statistically significant difference between the effectiveness of guidelines and patterns for new design. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for redesign and new design. Guidelines and patterns were found to be used in similar ways for design. There was no statistically significant difference between the perceived usefulness of the format, content, ease of learning, and usefulness as personal and shared design languages, of guidelines and patterns. Both participant groups were equally agreeable to using guidelines and patterns in the future. The perceived usefulness of pattern collections was found to depend on the usability of the collection interface and the content quality of the patterns. The results of the empirical study thus provided empirical evidence that patterns were as useful as guidelines for evaluation and new design, and were perceived as positively as guidelines were. Patterns were found to be superior to guidelines for redesign. Patterns can therefore be used with a measure of confidence as early stage design aids for physical design and evaluation in the future. In addition to these findings, a number of opportunities for further research were identified.
- Full Text:
- Date Issued: 2009
Chang liver cell line as a model for Type II Diabetes in the liver and possible reversal of this condition by an indigenous medicinal plant
- Authors: Williams, Saralene Iona
- Date: 2009
- Subjects: Diabetes -- Alternative treatment , Medicinal plants , Traditional medicine , Liver -- Diseases
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10339 , http://hdl.handle.net/10948/d1016179
- Description: The incidence of Type 2 Diabetes Mellittus (T2DM) is increasing world wide. In Africa the limited access to health care and the insidious course of the disease lead to more severe illness and diabetic complications. There is a need to find alternative approaches to treatment and prevention that address the problems and needs of Africa. Sutherlandia frutescens (S.frutescens) is a traditional herbal plant with known anti-diabetic properties, the precise mechanism of action of S.frutescens is not known. In order to develop new approaches for treatment and prevention of T2DM the pathophysiology of T2DM must be understood. T2DM is the final outcome of a multi-organ disease characterized by early defects in muscle, adipocytes, hepatocytes and pancreatic β-cells. In this study the role of the liver was investigated because of its central role in glucose and lipid metabolism. It is hard to differentiate between all the influences in an in vivo model, so the aim of this study was to develop an in vitro model of T2DM in Chang liver cells and to determine if S.frutescens can reverse the state of insulin resistance in this model. Different culture media conditions were screened to identify a method that can be used as the T2DM model in Chang liver cells. Serum free medium (MCBD-201) supplemented with human diabetic serum, (2.5%-10%), high insulin concentrations (0.1μM-1μM), high fructose concentrations (1-10mM). and a combination of high insulin and high fructose was used for this screening. Chang liver cells cultured in MCBD-201 medium supplemented with 1mM fructose and 0.1μM insulin showed reduced glucose uptake and increased lipid accumulation. The effect of two S.frutescens extracts, two anti-diabetic drugs, metformin and ciglitazone, and a hypolipidemic drug ciprofibrate were determined and shown to increase glucose uptake and reduce lipid accumulation. It was postulated that exposing the cells to excess nutrients in the form of high fructose would stimulate the cells to become adipogenic and accumulate lipids, which would interfere with the glucose uptake and induce insulin resistance. Gene expression of PPARγ, PPARα, and SREBP-1 transcription factors regulating lipid metabolism was determined in Chang liver cells cultured in insulin resistance inducing medium over a 48 hour time course. The expression of PPARγ, known to stimulate adipogenesis was increased after 6, 24 and 48 hours of exposure (P(H1)<0.0001). The expression of PPARα, known to stimulate β-oxidation expression, was significantly decreased after 24 hours of exposure (P(H1)<0.0001). The presence of the plant extracts in the insulin resistance inducing media protect against this increase in adipogenesis and decrease in β-oxidation after 48 hours of exposure by increasing PPARα expression and decreasing PPARγ expression. A PCR Array was performed which identified 32 more potential molecular targets of S.frutescens. Five of the 32 targets identified with the PCR Array were validated using qRT-PCR. These genes play a role in lipid and glucose metabolism and protection against oxidative stress and inflammation. In summary a cellular model of insulin resistace in hepatocytes has been established and the capacity of S.frutescens to reverse this process has been demonstrated by acting as a dual PPARγ/α agonist. New genes have been identified in the development of insulin resistance and as targets of S.frutescens.
- Full Text:
- Date Issued: 2009
- Authors: Williams, Saralene Iona
- Date: 2009
- Subjects: Diabetes -- Alternative treatment , Medicinal plants , Traditional medicine , Liver -- Diseases
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10339 , http://hdl.handle.net/10948/d1016179
- Description: The incidence of Type 2 Diabetes Mellittus (T2DM) is increasing world wide. In Africa the limited access to health care and the insidious course of the disease lead to more severe illness and diabetic complications. There is a need to find alternative approaches to treatment and prevention that address the problems and needs of Africa. Sutherlandia frutescens (S.frutescens) is a traditional herbal plant with known anti-diabetic properties, the precise mechanism of action of S.frutescens is not known. In order to develop new approaches for treatment and prevention of T2DM the pathophysiology of T2DM must be understood. T2DM is the final outcome of a multi-organ disease characterized by early defects in muscle, adipocytes, hepatocytes and pancreatic β-cells. In this study the role of the liver was investigated because of its central role in glucose and lipid metabolism. It is hard to differentiate between all the influences in an in vivo model, so the aim of this study was to develop an in vitro model of T2DM in Chang liver cells and to determine if S.frutescens can reverse the state of insulin resistance in this model. Different culture media conditions were screened to identify a method that can be used as the T2DM model in Chang liver cells. Serum free medium (MCBD-201) supplemented with human diabetic serum, (2.5%-10%), high insulin concentrations (0.1μM-1μM), high fructose concentrations (1-10mM). and a combination of high insulin and high fructose was used for this screening. Chang liver cells cultured in MCBD-201 medium supplemented with 1mM fructose and 0.1μM insulin showed reduced glucose uptake and increased lipid accumulation. The effect of two S.frutescens extracts, two anti-diabetic drugs, metformin and ciglitazone, and a hypolipidemic drug ciprofibrate were determined and shown to increase glucose uptake and reduce lipid accumulation. It was postulated that exposing the cells to excess nutrients in the form of high fructose would stimulate the cells to become adipogenic and accumulate lipids, which would interfere with the glucose uptake and induce insulin resistance. Gene expression of PPARγ, PPARα, and SREBP-1 transcription factors regulating lipid metabolism was determined in Chang liver cells cultured in insulin resistance inducing medium over a 48 hour time course. The expression of PPARγ, known to stimulate adipogenesis was increased after 6, 24 and 48 hours of exposure (P(H1)<0.0001). The expression of PPARα, known to stimulate β-oxidation expression, was significantly decreased after 24 hours of exposure (P(H1)<0.0001). The presence of the plant extracts in the insulin resistance inducing media protect against this increase in adipogenesis and decrease in β-oxidation after 48 hours of exposure by increasing PPARα expression and decreasing PPARγ expression. A PCR Array was performed which identified 32 more potential molecular targets of S.frutescens. Five of the 32 targets identified with the PCR Array were validated using qRT-PCR. These genes play a role in lipid and glucose metabolism and protection against oxidative stress and inflammation. In summary a cellular model of insulin resistace in hepatocytes has been established and the capacity of S.frutescens to reverse this process has been demonstrated by acting as a dual PPARγ/α agonist. New genes have been identified in the development of insulin resistance and as targets of S.frutescens.
- Full Text:
- Date Issued: 2009
Compensation for polarization mode dispersion and nonlinear birefringence in a multichannel optical fibre system
- Authors: Waswa, David Wafula
- Date: 2009
- Subjects: Fiber optics , Nonlinear optics , Polarization (Light)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10375 , http://hdl.handle.net/10948/885 , Fiber optics , Nonlinear optics , Polarization (Light)
- Description: Polarization mode dispersion (PMD) is stochastic in nature and continues evolving in an unpredictable manner according to the changing environment. Nonlinear birefringence in multichannel systems alters the polarization states of the bits, so that they vary from one bit to the next in a way that is difficult to predict. These are the two major signal-impairment effects that are inherent in optical fibre transmission links which can seriously degrade network performance. It is therefore extremely challenging to compensate for both linear and nonlinear birefringence in multichannel systems. The purpose of this thesis is to investigate the interaction between PMD and nonlinear induced birefringence in a fibre with consideration of mode coupling. A sound knowledge of this interaction is necessary in designing a linear and nonlinear polarization mode dispersion compensator for WDM systems, as was successfully carried out in this study. The investigation shows that the effect of nonlinear birefringence alone depolarizes the signal, while in high PMD links where polarization mode coupling is high, the nonlinear birefringence effect couples with second-order PMD such that it may reduce the penalty and improve the signal DOP. Further investigation shows that when nonlinear birefringence becomes significant, asymmetry arises between the two principal axes of the fibre, such that it is only one axis which experiences the effect of nonlinear birefringence. It is found out that along this vii axis, there exists a critical point in pump power where the nonlinear birefringence cancels PMD in the link and improves the signal. An adaptive compensator to cancel PMD and nonlinear birefringence was designed based on feedforward DOP-monitoring signal. The compensator was tested both at laboratory level and on the Telkom buried fibre link and found to be functioning as intended. It was able to adaptively track and compensate PMD in the link in less than a second. The compensator was able to cancel PMD in the link up to a maximum of 30 ps. The compensator improved the DOP of the worst signal by more than 100 percent.
- Full Text:
- Date Issued: 2009
- Authors: Waswa, David Wafula
- Date: 2009
- Subjects: Fiber optics , Nonlinear optics , Polarization (Light)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10375 , http://hdl.handle.net/10948/885 , Fiber optics , Nonlinear optics , Polarization (Light)
- Description: Polarization mode dispersion (PMD) is stochastic in nature and continues evolving in an unpredictable manner according to the changing environment. Nonlinear birefringence in multichannel systems alters the polarization states of the bits, so that they vary from one bit to the next in a way that is difficult to predict. These are the two major signal-impairment effects that are inherent in optical fibre transmission links which can seriously degrade network performance. It is therefore extremely challenging to compensate for both linear and nonlinear birefringence in multichannel systems. The purpose of this thesis is to investigate the interaction between PMD and nonlinear induced birefringence in a fibre with consideration of mode coupling. A sound knowledge of this interaction is necessary in designing a linear and nonlinear polarization mode dispersion compensator for WDM systems, as was successfully carried out in this study. The investigation shows that the effect of nonlinear birefringence alone depolarizes the signal, while in high PMD links where polarization mode coupling is high, the nonlinear birefringence effect couples with second-order PMD such that it may reduce the penalty and improve the signal DOP. Further investigation shows that when nonlinear birefringence becomes significant, asymmetry arises between the two principal axes of the fibre, such that it is only one axis which experiences the effect of nonlinear birefringence. It is found out that along this vii axis, there exists a critical point in pump power where the nonlinear birefringence cancels PMD in the link and improves the signal. An adaptive compensator to cancel PMD and nonlinear birefringence was designed based on feedforward DOP-monitoring signal. The compensator was tested both at laboratory level and on the Telkom buried fibre link and found to be functioning as intended. It was able to adaptively track and compensate PMD in the link in less than a second. The compensator was able to cancel PMD in the link up to a maximum of 30 ps. The compensator improved the DOP of the worst signal by more than 100 percent.
- Full Text:
- Date Issued: 2009
Development of a process for the preparation of linalool from CIS-2-pinanol
- Authors: Buddoo, Subash Ramnarain
- Date: 2009
- Subjects: Odors , Perfumes -- History , Perfumes -- Formulae , Fermentation
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10425 , http://hdl.handle.net/10948/d1016219
- Description: Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis-2-pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis-2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis-2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis-2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis-2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by theclient for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8 percent between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng).
- Full Text:
- Date Issued: 2009
- Authors: Buddoo, Subash Ramnarain
- Date: 2009
- Subjects: Odors , Perfumes -- History , Perfumes -- Formulae , Fermentation
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10425 , http://hdl.handle.net/10948/d1016219
- Description: Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis-2-pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis-2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis-2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis-2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis-2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by theclient for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8 percent between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng).
- Full Text:
- Date Issued: 2009
Ecological role of estuarine brachyuran crabs in mangrove and salt marsh estuaries, Eastern Cape, South Africa
- Authors: Vorsatz, Jeanne Pauline
- Date: 2009
- Subjects: Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10698 , http://hdl.handle.net/10948/1108 , Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Description: Crabs are conspicuous inhabitants of temperate salt marshes and tropical mangroves and interact with their environment through several processes. However, detailed information on crab community processes is absent for most South African estuaries and nearshore coastal regions. This study evaluated the primary producers supporting crab species in the salt marsh dominated Swartkops estuary and the mangrove Mngazana estuary. Various methods estimating crab abundances were also assessed in different microhabitats and the larval distribution of crabs in the coastal zone was also investigated. Various methods for estimating crab abundance have been employed in the past, each with its inherent biases. The microhabitat of a mangrove forest in Australia was structurally altered by the manipulation of the litter, pneumatophores and the associated algae. These alterations did not affect the behavioural activity or the numbers of crabs recorded in any of the experimental treatments by either visual counts or pitfall traps. However, the number of crabs caught in the pitfall traps differed between the sites. Species-specific behaviour which was not investigated in this study may bias crab abundance estimates when using pitfall traps and therefore requires further investigation. Benthic consumers inhabiting shallow coastal environments may ultimately have the origin of their nutrition in a number of possible sources. Isotopic and gut content analysis of Thalamita crenata and juvenile Scylla serrata in the Mngazana estuary in South Africa revealed that these two portunids are able to share a habitat by resource partitioning. Differences were noted for species-specific utilization of primary producers not only between seasons within a site, but also between sites. This highlighted the use of locally produced primary producers sustaining food webs in estuaries. Mangrove production in the Mngazana estuary is very important and contributes to most of the carbon in the underlying sediments in the mangrove forest. However, the relatively large number of species and biomass encountered in this estuary may also be attributed to the fact that the different species are able to exploit of a number of different resources. The variation in stable isotope analysis of the different crab species throughout the estuary indicated that these crabs able to occupy the same habitat by feeding on a number of different resources and may preferentially select for a specific primary producer. A stable isotope of crabs in the salt marsh Swartkops estuary indicated that the dominant primary producer sustaining crab communities may even take place on a relatively smallscale. Sesarma catenata found at the inner marsh site recorded more depleted carbon signatures than those encountered in the other sites approximately 100 m away, and reflected signatures similar to the locally-encountered inner marsh plants. The relatively enriched nitrogen signatures of the anthropogenically-impacted Swartkops estuary is an indication of extensive inputs due to urbanization and industrialization, in contrast to the relatively pristine Mngazana estuary which exhibited low nitrogen signatures. Emphasis has been placed on the abiotic component of the exchange of nutrients and energy, although living organisms may also be transported, both actively and passively, between ecosystems. Little variation in either species composition or abundance was found between seasons for the larval distribution of brachyuran crabs on the east coast of South Africa. Due to the lack of published larval descriptions, larvae could not be identified to species level and it was therefore not possible to identify whether the larvae were hatched or spawned in an estuary or in a marine environment, or whether the larvae originated in the northern tropical regions. Frequent wind-reversals which are common in this region may retain larvae close inshore and supply the southern temperate locations with larvae from the northern locations. In conclusion, this study has shown that in highly productive systems with a number of potential primary producers, the crabs that inhabit the estuary show a marked diversity in resource utilization which could potentially allow a number of closely related species to occupy different trophic levels. This study also highlights the importance of locally produced sources in an estuary, which may occur on very small scales and this needs to be factored in with the design of any future stable isotope studies of this nature.
- Full Text:
- Date Issued: 2009
- Authors: Vorsatz, Jeanne Pauline
- Date: 2009
- Subjects: Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10698 , http://hdl.handle.net/10948/1108 , Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Description: Crabs are conspicuous inhabitants of temperate salt marshes and tropical mangroves and interact with their environment through several processes. However, detailed information on crab community processes is absent for most South African estuaries and nearshore coastal regions. This study evaluated the primary producers supporting crab species in the salt marsh dominated Swartkops estuary and the mangrove Mngazana estuary. Various methods estimating crab abundances were also assessed in different microhabitats and the larval distribution of crabs in the coastal zone was also investigated. Various methods for estimating crab abundance have been employed in the past, each with its inherent biases. The microhabitat of a mangrove forest in Australia was structurally altered by the manipulation of the litter, pneumatophores and the associated algae. These alterations did not affect the behavioural activity or the numbers of crabs recorded in any of the experimental treatments by either visual counts or pitfall traps. However, the number of crabs caught in the pitfall traps differed between the sites. Species-specific behaviour which was not investigated in this study may bias crab abundance estimates when using pitfall traps and therefore requires further investigation. Benthic consumers inhabiting shallow coastal environments may ultimately have the origin of their nutrition in a number of possible sources. Isotopic and gut content analysis of Thalamita crenata and juvenile Scylla serrata in the Mngazana estuary in South Africa revealed that these two portunids are able to share a habitat by resource partitioning. Differences were noted for species-specific utilization of primary producers not only between seasons within a site, but also between sites. This highlighted the use of locally produced primary producers sustaining food webs in estuaries. Mangrove production in the Mngazana estuary is very important and contributes to most of the carbon in the underlying sediments in the mangrove forest. However, the relatively large number of species and biomass encountered in this estuary may also be attributed to the fact that the different species are able to exploit of a number of different resources. The variation in stable isotope analysis of the different crab species throughout the estuary indicated that these crabs able to occupy the same habitat by feeding on a number of different resources and may preferentially select for a specific primary producer. A stable isotope of crabs in the salt marsh Swartkops estuary indicated that the dominant primary producer sustaining crab communities may even take place on a relatively smallscale. Sesarma catenata found at the inner marsh site recorded more depleted carbon signatures than those encountered in the other sites approximately 100 m away, and reflected signatures similar to the locally-encountered inner marsh plants. The relatively enriched nitrogen signatures of the anthropogenically-impacted Swartkops estuary is an indication of extensive inputs due to urbanization and industrialization, in contrast to the relatively pristine Mngazana estuary which exhibited low nitrogen signatures. Emphasis has been placed on the abiotic component of the exchange of nutrients and energy, although living organisms may also be transported, both actively and passively, between ecosystems. Little variation in either species composition or abundance was found between seasons for the larval distribution of brachyuran crabs on the east coast of South Africa. Due to the lack of published larval descriptions, larvae could not be identified to species level and it was therefore not possible to identify whether the larvae were hatched or spawned in an estuary or in a marine environment, or whether the larvae originated in the northern tropical regions. Frequent wind-reversals which are common in this region may retain larvae close inshore and supply the southern temperate locations with larvae from the northern locations. In conclusion, this study has shown that in highly productive systems with a number of potential primary producers, the crabs that inhabit the estuary show a marked diversity in resource utilization which could potentially allow a number of closely related species to occupy different trophic levels. This study also highlights the importance of locally produced sources in an estuary, which may occur on very small scales and this needs to be factored in with the design of any future stable isotope studies of this nature.
- Full Text:
- Date Issued: 2009
Immobilization of catalyst in a wall-coated micro-structured reactor for gas/liquid oxidation of p-cymene
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
Investigation of device and performance parameters of photovoltaic devices
- Macabebe, Erees Queen Barrido
- Authors: Macabebe, Erees Queen Barrido
- Date: 2009
- Subjects: Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10538 , http://hdl.handle.net/10948/1003 , http://hdl.handle.net/10948/d1012890 , Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Description: In order to investigate the influence of parasitic resistances, saturation current and diode ideality factor on the performance of photovoltaic devices, parameter extraction routines employing the standard iteration (SI) method and the particle swarm optimization (PSO) method were developed to extract the series resistance, shunt resistance, saturation current and ideality factor from the I-V characteristics of solar cells and PV modules. The well-known one- and two-diode models were used to describe the behavior of the I-V curve and the parameters of the models were determined by approximation and iteration techniques. The SI and the PSO extraction programmes were used to assess the suitability of the one- and the two-diode solar cell models in describing the I-V characteristics of mono- and multicrystalline silicon solar cells, CISS- and CIGSS-based solar cells. This exercise revealed that the two-diode model provides more information regarding the different processes involved in solar cell operation. Between the two methods developed, the PSO method is faster, yielded fitted curves with lower standard deviation of residuals and, therefore, was the preferred extraction method. The PSO method was then used to extract the device parameters of CISS-based solar cells with the CISS layer selenized under different selenization process conditions and CIGSS-based solar cells with varying i-ZnO layer thickness. For the CISS-based solar cells, the detrimental effect of parasitic resistances on device performance increased when the temperature and duration of the selenization process was increased. For the CIGSS-based devices, photogeneration improved with increasing i-ZnO layer thickness. At high forward bias, bulk recombination and/or tunneling-assisted recombination were the dominant processes affecting the I-V characteristics of the devices. v Lastly, device and performance parameters of mono-, multicrystalline silicon and CIS modules derived from I-V characteristics obtained under dark and illuminated conditions were analyzed considering the effects of temperature on the performance of the devices. Results showed that the effects of parasitic resistances are greater under illumination and, under outdoor conditions, the values further declined due to increasing temperature. The saturation current and ideality factor also increased under outdoor conditions which suggest increased recombination and, coupled with the adverse effects of parasitic resistances, these factors result in lower FF and lower maximum power point. Analysis performed on crystalline silicon and thin film devices utilized in this study revealed that parameter extraction from I-V characteristics of photovoltaic devices and, in particular, the implementation of PSO in solar cell device parameter extraction developed in this work is a useful characterization technique.
- Full Text:
- Date Issued: 2009
- Authors: Macabebe, Erees Queen Barrido
- Date: 2009
- Subjects: Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10538 , http://hdl.handle.net/10948/1003 , http://hdl.handle.net/10948/d1012890 , Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Description: In order to investigate the influence of parasitic resistances, saturation current and diode ideality factor on the performance of photovoltaic devices, parameter extraction routines employing the standard iteration (SI) method and the particle swarm optimization (PSO) method were developed to extract the series resistance, shunt resistance, saturation current and ideality factor from the I-V characteristics of solar cells and PV modules. The well-known one- and two-diode models were used to describe the behavior of the I-V curve and the parameters of the models were determined by approximation and iteration techniques. The SI and the PSO extraction programmes were used to assess the suitability of the one- and the two-diode solar cell models in describing the I-V characteristics of mono- and multicrystalline silicon solar cells, CISS- and CIGSS-based solar cells. This exercise revealed that the two-diode model provides more information regarding the different processes involved in solar cell operation. Between the two methods developed, the PSO method is faster, yielded fitted curves with lower standard deviation of residuals and, therefore, was the preferred extraction method. The PSO method was then used to extract the device parameters of CISS-based solar cells with the CISS layer selenized under different selenization process conditions and CIGSS-based solar cells with varying i-ZnO layer thickness. For the CISS-based solar cells, the detrimental effect of parasitic resistances on device performance increased when the temperature and duration of the selenization process was increased. For the CIGSS-based devices, photogeneration improved with increasing i-ZnO layer thickness. At high forward bias, bulk recombination and/or tunneling-assisted recombination were the dominant processes affecting the I-V characteristics of the devices. v Lastly, device and performance parameters of mono-, multicrystalline silicon and CIS modules derived from I-V characteristics obtained under dark and illuminated conditions were analyzed considering the effects of temperature on the performance of the devices. Results showed that the effects of parasitic resistances are greater under illumination and, under outdoor conditions, the values further declined due to increasing temperature. The saturation current and ideality factor also increased under outdoor conditions which suggest increased recombination and, coupled with the adverse effects of parasitic resistances, these factors result in lower FF and lower maximum power point. Analysis performed on crystalline silicon and thin film devices utilized in this study revealed that parameter extraction from I-V characteristics of photovoltaic devices and, in particular, the implementation of PSO in solar cell device parameter extraction developed in this work is a useful characterization technique.
- Full Text:
- Date Issued: 2009
Mathematical requirements for first-year BCOM students at NMMU
- Authors: Walton, Marguerite
- Date: 2009
- Subjects: Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10502 , http://hdl.handle.net/10948/886 , Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Description: These studies have focused on identifying the mathematical requirements of first-year BCom students at Nelson Mandela Metropolitan University. The research methodology used in this quantitative study was to make use of interviewing, questionnaire investigation, and document analysis in the form of textbook, test and examination analysis. These methods provided data that fitted into a grounded theory approach. The study concluded by identifying the list of mathematical topics required for the first year of the core subjects in the BCom degree programme. In addition, the study found that learners who study Mathematics in the National Senior Certificate should be able to cope with the mathematical content included in their BCom degree programme, while learners studying Mathematical Literacy would probably need support in some of the areas of mathematics, especially algebra, in order to cope with the mathematical content included in their BCom degree programme. It makes a valuable contribution towards elucidating the mathematical requirements needed to improve the chances of successful BCom degree programme studies at South African universities. It also draws the contours for starting to design an efficient support course for future “at-risk” students who enter higher education studies.
- Full Text:
- Date Issued: 2009
- Authors: Walton, Marguerite
- Date: 2009
- Subjects: Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10502 , http://hdl.handle.net/10948/886 , Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Description: These studies have focused on identifying the mathematical requirements of first-year BCom students at Nelson Mandela Metropolitan University. The research methodology used in this quantitative study was to make use of interviewing, questionnaire investigation, and document analysis in the form of textbook, test and examination analysis. These methods provided data that fitted into a grounded theory approach. The study concluded by identifying the list of mathematical topics required for the first year of the core subjects in the BCom degree programme. In addition, the study found that learners who study Mathematics in the National Senior Certificate should be able to cope with the mathematical content included in their BCom degree programme, while learners studying Mathematical Literacy would probably need support in some of the areas of mathematics, especially algebra, in order to cope with the mathematical content included in their BCom degree programme. It makes a valuable contribution towards elucidating the mathematical requirements needed to improve the chances of successful BCom degree programme studies at South African universities. It also draws the contours for starting to design an efficient support course for future “at-risk” students who enter higher education studies.
- Full Text:
- Date Issued: 2009
New platinum coordination compounds : their synthesis, characterization and anticancer application
- Authors: Oosthuizen, Lukas Marthinus
- Date: 2009
- Subjects: Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10430 , http://hdl.handle.net/10948/d1018795
- Description: The aim of this thesis was to investigate the properties of novel platinum compounds with possible potential as anticancer agents, and to determine how their behaviour could lead to a better understanding of the chemistry involved. The final criteria were improvement of their anticancer behaviour. Since many questions are still unanswered as to the role of sulfur in anticancer action, studies were undertaken to synthesize novel platinum(II) complexes having non-leaving groups consisting of a combination of an aromatic nitrogen and thioetherial sulfur capable of forming a five membered ring upon coordination. The structural unit was 1-methyl-2-methylthioalkyl/aryl. Numerous complexes formed by these ligands each having chloro, bromo, iodo and oxalato leaving groups were then fully characterized. The results obtained by the various synthetic methods were compared and explained in terms of the chemistry involved. The role of the sulfur donor was indicated in both the halo- and oxalato-complexes and proved to be strongly influenced by the nature of the leaving groups. Their differences are reflected in their anticancer behaviour. The study was extended to mononitroplatinum(IV) complexes, in view of the kinetically stable platinum(IV) compounds and advantages related to this. A specific mononitroplatinum(IV) complex which proved to have good anticancer and STAT 3 properties could according to the literature not be synthesized successfully in a good yield and a high degree of purity. The results of extensive studies showed that the main problem centred around the simultaneous reactions in equilibrium during the synthesis. A number of these species formed as a result of side reactions could be identified and their close separation factors indicated chromatographically. The mechanism of these reactions and the unstable intermediate species involved could be rationalized and compared to analogues in the literature. All the complexes studied were characterized by spectral and thermal methods both in solution as well as the solid state. Their anticancer behaviour towards three anticancer cell lines (Hela, MCF 7, Ht 29) were determined and acted as a guide towards possible structural modifications for their improved capability. Three crystal structures of platinum(II) complexes were determined. The extent of the ionization of the platinum(II) complexes as well the redox potentials (Pt(II) / Pt(IV)) of the platinum(IV) complexes were particularly important factors pertaining to their anticancer action.
- Full Text:
- Date Issued: 2009
- Authors: Oosthuizen, Lukas Marthinus
- Date: 2009
- Subjects: Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10430 , http://hdl.handle.net/10948/d1018795
- Description: The aim of this thesis was to investigate the properties of novel platinum compounds with possible potential as anticancer agents, and to determine how their behaviour could lead to a better understanding of the chemistry involved. The final criteria were improvement of their anticancer behaviour. Since many questions are still unanswered as to the role of sulfur in anticancer action, studies were undertaken to synthesize novel platinum(II) complexes having non-leaving groups consisting of a combination of an aromatic nitrogen and thioetherial sulfur capable of forming a five membered ring upon coordination. The structural unit was 1-methyl-2-methylthioalkyl/aryl. Numerous complexes formed by these ligands each having chloro, bromo, iodo and oxalato leaving groups were then fully characterized. The results obtained by the various synthetic methods were compared and explained in terms of the chemistry involved. The role of the sulfur donor was indicated in both the halo- and oxalato-complexes and proved to be strongly influenced by the nature of the leaving groups. Their differences are reflected in their anticancer behaviour. The study was extended to mononitroplatinum(IV) complexes, in view of the kinetically stable platinum(IV) compounds and advantages related to this. A specific mononitroplatinum(IV) complex which proved to have good anticancer and STAT 3 properties could according to the literature not be synthesized successfully in a good yield and a high degree of purity. The results of extensive studies showed that the main problem centred around the simultaneous reactions in equilibrium during the synthesis. A number of these species formed as a result of side reactions could be identified and their close separation factors indicated chromatographically. The mechanism of these reactions and the unstable intermediate species involved could be rationalized and compared to analogues in the literature. All the complexes studied were characterized by spectral and thermal methods both in solution as well as the solid state. Their anticancer behaviour towards three anticancer cell lines (Hela, MCF 7, Ht 29) were determined and acted as a guide towards possible structural modifications for their improved capability. Three crystal structures of platinum(II) complexes were determined. The extent of the ionization of the platinum(II) complexes as well the redox potentials (Pt(II) / Pt(IV)) of the platinum(IV) complexes were particularly important factors pertaining to their anticancer action.
- Full Text:
- Date Issued: 2009
Patterns and determinants of species richness in mesic temparate grasslands of South Africa
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
Polarization mode dispersion emulation and the impact of high first-order PMD segments in optical telecommunication systems
- Authors: Musara, Vitalis
- Date: 2009
- Subjects: Optical communications , Fiber optics , Polarization (Light)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10519 , http://hdl.handle.net/10948/1138 , Optical communications , Fiber optics , Polarization (Light)
- Description: In this study, focus is centred on the measurement and emulation of first-order (FO-) and second-order (SO-) polarization mode dispersion (PMD). PMD has deleterious effects on the performance of high speed optical transmission network systems from 10 Gb/s and above. The first step was characterising deployed fibres for PMD and monitoring the state of polarization (SOP) light experiences as it propagates through the fibre. The PMD and SOP changes in deployed fibres were stochastic due to varying intrinsic and extrinsic perturbation changes. To fully understand the PMD phenomenon in terms of measurement accuracy, its complex behaviour, its implications, mitigation and compensation, PMD emulation is crucial. This thesis presents emulator designs which fall into different emulator categories. The key to these designs were the PMD equations and background on the PMD phenomenon. The cross product from the concatenation equation was applied in order to determine the coupling angle β (between 0o and 180o) that results in the SO-PMD of the emulator designs to be either adjustable or fixed. The digital delay line (DDL) or single polarization maintaining fibre (PMF) section was used to give a certain amount of FO-PMD but negligible SO-PMD. PMF sections (birefringent sections) were concatenated together to ensure FO- and SO-PMD coexist, emulating deployed fibres. FO- and SO-PMD can be controlled by altering mode coupling (coupling angles) and birefringence distribution. Emulators with PMD statistics approaching the theoretical distributions had high random coupling and several numbers of randomly distributed PMF sections. In addition, the lengths of their PMF sections lie within 20% standard deviation of the mean emulator length. Those emulators with PMD statistics that did not approach the theoretical distributions had limited numbers of randomly distributed PMF sections and mode coupling. Results also show that even when an emulator has high random mode coupling and several numbers of randomly distributed PMFs, its PMD statistics deviates away from expected theoretical distributions in the presence of polarization dependent loss (PDL). The emulators showed that the background autocorrelation function (BACF) approaches zero with increasing number of randomly mode coupled fibre sections. A zero BACF signifies that an emulator has large numbers of randomly distributed PMF sections and its presence means the opposite. The availability of SO-PMD in the emulators made the autocorrelation function (ACF) x asymmetric. In the absence of SO-PMD the ACF for a PMD emulator is symmetric. SO-PMD has no effect on the BACF. Polarization-optical time domain reflectometry (P-OTDR) measurements have shown that certain fibre sections along fibre link lengths have higher FO-PMD (HiFO-PMD) than other sections. This study investigates the impact of a HiFO-PMD section on the overall FO- and SO-PMD, the output state of polarization (SOP) and system performance on deployed fibres (through emulation). Results show that when the wavelength-independent FO-PMD vector of the HiFO-PMD section is greater than the FO-PMD contributions from the rest of the fibre link, the mean FO-PMD of the entire link is biased towards that of the HiFO-PMD section and the SO-PMD increases (β ≠ 0o or 180o) or remains fixed (β = 0o or 180o) depending on the coupling angle β between the HiFO-PMD section and the rest of the fibre link. In addition, the FO-PMD statistics deviates away from the theoretical Maxwellian distribution. However, experimental results show that the HiFO-PMD section has negligible influence on the SOPMD statistical distribution. An increase in the amount of FO-PMD on a HiFO-PMD section reduces the output SOP spread to a given minimum, in this study the minimum was reached when the HiFO-PMD ≥ 35 ps. However, the outcome of the output SOP spread depends on the location of the HiFO-PMD section along the fibre link length. It was found that when the HiFO-PMD section introduces SO-PMD, the bit error rate (BER) is much higher compared to when it does not introduce SO-PMD.
- Full Text:
- Date Issued: 2009
- Authors: Musara, Vitalis
- Date: 2009
- Subjects: Optical communications , Fiber optics , Polarization (Light)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10519 , http://hdl.handle.net/10948/1138 , Optical communications , Fiber optics , Polarization (Light)
- Description: In this study, focus is centred on the measurement and emulation of first-order (FO-) and second-order (SO-) polarization mode dispersion (PMD). PMD has deleterious effects on the performance of high speed optical transmission network systems from 10 Gb/s and above. The first step was characterising deployed fibres for PMD and monitoring the state of polarization (SOP) light experiences as it propagates through the fibre. The PMD and SOP changes in deployed fibres were stochastic due to varying intrinsic and extrinsic perturbation changes. To fully understand the PMD phenomenon in terms of measurement accuracy, its complex behaviour, its implications, mitigation and compensation, PMD emulation is crucial. This thesis presents emulator designs which fall into different emulator categories. The key to these designs were the PMD equations and background on the PMD phenomenon. The cross product from the concatenation equation was applied in order to determine the coupling angle β (between 0o and 180o) that results in the SO-PMD of the emulator designs to be either adjustable or fixed. The digital delay line (DDL) or single polarization maintaining fibre (PMF) section was used to give a certain amount of FO-PMD but negligible SO-PMD. PMF sections (birefringent sections) were concatenated together to ensure FO- and SO-PMD coexist, emulating deployed fibres. FO- and SO-PMD can be controlled by altering mode coupling (coupling angles) and birefringence distribution. Emulators with PMD statistics approaching the theoretical distributions had high random coupling and several numbers of randomly distributed PMF sections. In addition, the lengths of their PMF sections lie within 20% standard deviation of the mean emulator length. Those emulators with PMD statistics that did not approach the theoretical distributions had limited numbers of randomly distributed PMF sections and mode coupling. Results also show that even when an emulator has high random mode coupling and several numbers of randomly distributed PMFs, its PMD statistics deviates away from expected theoretical distributions in the presence of polarization dependent loss (PDL). The emulators showed that the background autocorrelation function (BACF) approaches zero with increasing number of randomly mode coupled fibre sections. A zero BACF signifies that an emulator has large numbers of randomly distributed PMF sections and its presence means the opposite. The availability of SO-PMD in the emulators made the autocorrelation function (ACF) x asymmetric. In the absence of SO-PMD the ACF for a PMD emulator is symmetric. SO-PMD has no effect on the BACF. Polarization-optical time domain reflectometry (P-OTDR) measurements have shown that certain fibre sections along fibre link lengths have higher FO-PMD (HiFO-PMD) than other sections. This study investigates the impact of a HiFO-PMD section on the overall FO- and SO-PMD, the output state of polarization (SOP) and system performance on deployed fibres (through emulation). Results show that when the wavelength-independent FO-PMD vector of the HiFO-PMD section is greater than the FO-PMD contributions from the rest of the fibre link, the mean FO-PMD of the entire link is biased towards that of the HiFO-PMD section and the SO-PMD increases (β ≠ 0o or 180o) or remains fixed (β = 0o or 180o) depending on the coupling angle β between the HiFO-PMD section and the rest of the fibre link. In addition, the FO-PMD statistics deviates away from the theoretical Maxwellian distribution. However, experimental results show that the HiFO-PMD section has negligible influence on the SOPMD statistical distribution. An increase in the amount of FO-PMD on a HiFO-PMD section reduces the output SOP spread to a given minimum, in this study the minimum was reached when the HiFO-PMD ≥ 35 ps. However, the outcome of the output SOP spread depends on the location of the HiFO-PMD section along the fibre link length. It was found that when the HiFO-PMD section introduces SO-PMD, the bit error rate (BER) is much higher compared to when it does not introduce SO-PMD.
- Full Text:
- Date Issued: 2009
Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
The coordination chemistry of Rhenium(V) with multidentate no-donor ligands
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
The development and evaluation of gaze selection techniques
- Authors: Van Tonder, Martin Stephen
- Date: 2009
- Subjects: Human-computer interaction , User interfaces (Computer systems) , Gaze
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10469 , http://hdl.handle.net/10948/882 , Human-computer interaction , User interfaces (Computer systems) , Gaze
- Description: Eye gaze interaction enables users to interact with computers using their eyes. A wide variety of eye gaze interaction techniques have been developed to support this type of interaction. Gaze selection techniques, a class of eye gaze interaction techniques which support target selection, are the subject of this research. Researchers developing these techniques face a number of challenges. The most significant challenge is the limited accuracy of eye tracking equipment (due to the properties of the human eye). The design of gaze selection techniques is dominated by this constraint. Despite decades of research, existing techniques are still significantly less accurate than the mouse. A recently developed technique, EyePoint, represents the state of the art in gaze selection techniques. EyePoint combines gaze input with keyboard input. Evaluation results for this technique are encouraging, but accuracy is still a concern. Early trigger errors, resulting from users triggering a selection before looking at the intended target, were found to be the most commonly occurring errors for this technique. The primary goal of this research was to improve the usability of gaze selection techniques. In order to achieve this goal, novel gaze selection techniques were developed. New techniques were developed by combining elements of existing techniques in novel ways. Seven novel gaze selection techniques were developed. Three of these techniques were selected for evaluation. A software framework was developed for implementing and evaluating gaze selection techniques. This framework was used to implement the gaze selection techniques developed during this research. Implementing and evaluating all of the techniques using a common framework ensured consistency when comparing the techniques. The novel techniques which were developed were evaluated against EyePoint and the mouse using the framework. The three novel techniques evaluated were named TargetPoint, StaggerPoint and ScanPoint. TargetPoint combines motor space expansion with a visual feedback highlight whereas the StaggerPoint and TargetPoint designs explore novel approaches to target selection disambiguation. A usability evaluation of the three novel techniques alongside EyePoint and the mouse revealed some interesting trends. TargetPoint was found to be more usable and accurate than EyePoint. This novel technique also proved more popular with test participants. One aspect of TargetPoint which proved particularly popular was the visual feedback highlight, a feature which was found to be a more effective method of combating early trigger errors than existing approaches. StaggerPoint was more efficient than EyePoint, but was less effective and satisfying. ScanPoint was the least popular technique. The benefits of providing a visual feedback highlight and test participants' positive views thereof contradict views expressed in existing research regarding the usability of visual feedback. These results have implications for the design of future gaze selection techniques. A set of design principles was developed for designing new gaze selection techniques. The designers of gaze selection techniques can benefit from these design principles by applying them to their techniques
- Full Text:
- Date Issued: 2009
- Authors: Van Tonder, Martin Stephen
- Date: 2009
- Subjects: Human-computer interaction , User interfaces (Computer systems) , Gaze
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10469 , http://hdl.handle.net/10948/882 , Human-computer interaction , User interfaces (Computer systems) , Gaze
- Description: Eye gaze interaction enables users to interact with computers using their eyes. A wide variety of eye gaze interaction techniques have been developed to support this type of interaction. Gaze selection techniques, a class of eye gaze interaction techniques which support target selection, are the subject of this research. Researchers developing these techniques face a number of challenges. The most significant challenge is the limited accuracy of eye tracking equipment (due to the properties of the human eye). The design of gaze selection techniques is dominated by this constraint. Despite decades of research, existing techniques are still significantly less accurate than the mouse. A recently developed technique, EyePoint, represents the state of the art in gaze selection techniques. EyePoint combines gaze input with keyboard input. Evaluation results for this technique are encouraging, but accuracy is still a concern. Early trigger errors, resulting from users triggering a selection before looking at the intended target, were found to be the most commonly occurring errors for this technique. The primary goal of this research was to improve the usability of gaze selection techniques. In order to achieve this goal, novel gaze selection techniques were developed. New techniques were developed by combining elements of existing techniques in novel ways. Seven novel gaze selection techniques were developed. Three of these techniques were selected for evaluation. A software framework was developed for implementing and evaluating gaze selection techniques. This framework was used to implement the gaze selection techniques developed during this research. Implementing and evaluating all of the techniques using a common framework ensured consistency when comparing the techniques. The novel techniques which were developed were evaluated against EyePoint and the mouse using the framework. The three novel techniques evaluated were named TargetPoint, StaggerPoint and ScanPoint. TargetPoint combines motor space expansion with a visual feedback highlight whereas the StaggerPoint and TargetPoint designs explore novel approaches to target selection disambiguation. A usability evaluation of the three novel techniques alongside EyePoint and the mouse revealed some interesting trends. TargetPoint was found to be more usable and accurate than EyePoint. This novel technique also proved more popular with test participants. One aspect of TargetPoint which proved particularly popular was the visual feedback highlight, a feature which was found to be a more effective method of combating early trigger errors than existing approaches. StaggerPoint was more efficient than EyePoint, but was less effective and satisfying. ScanPoint was the least popular technique. The benefits of providing a visual feedback highlight and test participants' positive views thereof contradict views expressed in existing research regarding the usability of visual feedback. These results have implications for the design of future gaze selection techniques. A set of design principles was developed for designing new gaze selection techniques. The designers of gaze selection techniques can benefit from these design principles by applying them to their techniques
- Full Text:
- Date Issued: 2009
The development of a commercial production process for p-menthane-3,8-diol
- Authors: Rust, Nico
- Date: 2009
- Subjects: Insect pests -- Control , Repellents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10427 , http://hdl.handle.net/10948/d1018273
- Description: The synthesis of p-menthane-3,8-diol via the acid-catalyzed cyclization of citronellal in a dilute aqueous sulphuric acid medium was investigated using conventional batch and continuous systems in order to develop a commercial production process for said p-menthane-3,8-diol (PMD). The batch studies conducted during the first part of this study showed that the formation of PMD from citronellal occurs via an intra-molecular Prins reaction that results in the formation of both the desired PMD product, as well as the partially hydrated isopulegol. It was shown that the formationof the by- product, PMD-acetal, results from the reaction between an intermediate, 5-methyl-2- isopropylcyclohexanol, and the citronellal starting material, and not from the reaction between PMD and citronellal as previously reported. Kinetic studies confirmed the existence of a complicated kinetic model. The formation of PMD from citronellal displayed typical pseudo first order kinetics up to conversions of 70 after which the kinetic model becomes complicated as the result of the establishment of quasi equilibrium reactions between PMD and isopulegol (dehydration of PMD and hydration of isopulegol) and between PMD the PMD-acetal, both systems being acid catalysed. The PMD-acetal formation reaction appears to be second order with respect to PMD. Scale-up studies of the batch process to 30L and 50L scales showed that it would be extremely difficult to limit the level of PMD-acetal formation below the desired level of 1 percent, even if citronellal conversions are restricted to about 50 percent. During studies conducted on a commercially availablemicro-structured organic synthesis plant (OSP) it was shown that it is possible to perform the PMD reaction as a continuous process. The results obtained showed that the use of a micro-mixer such as the caterpillar micro-mixer did not provide enough residence time in order for desirable conversions (- 40 percent) to be obtained. By combining themicro-mixer with delay-loops of different thicknesses and lengths, and using increasing reaction temperatures, it was shown that the conversion of citronellal could be improved to some extent, but compared poorly to the expected conversions for a well-stirred batch reactor. By packing selected delay loops with inert SiC particles, improved mass transfer was observed between the organic and aqueous phases as reflected in the increased conversion of citronellal. Using the observations that were made during the use of the OSP, a continuous-flow, tubular reactor system was designed and constructed. Advanced statistical techniques were used to investigate the effect of variables such as temperature, acid concentration, reactor length, flow rate and the organic to aqueous ratio on the rate and selectivity of the reaction. Mathematical models were derived for citronellal conversion, yield of PMD and yield of PMD- acetals, and used to predict the concentrations of citronellal, PMD and PMD-acetals at set experimental conditions. The results obtained showed that it was possible to obtain a product which approached desired specifications.Downstream processing of the PMD reaction mixture as it exits the reactor requires phase separation and neutralization of the acid catalyst solution, followed by further work-up to recover unreacted starting material and intermediates for recycle back to the synthesis reactor, followed by purification of crude PMD to the desired specification. The study showed that neutralization, prior or after phase separation, does not affect the selectivity of the PMD to such a great extent, but does influence the relative conversion due to extended contact of the catalyst with the organic phase after the reaction is terminated. Recovery of unreacted citronellal and isopulegol could be achieved by a simple vacuum evaporation step, which may either be carried out in a batch manner using traditional distillation equipment, or in a continuous process using wiped-film (short path) techniques. It was also shown that selective crystallization of PMD from the crude product mixture by addition of a solvent, such as heptanes or hexane proved to be the best way of achieving the desired product specification.
- Full Text:
- Date Issued: 2009
- Authors: Rust, Nico
- Date: 2009
- Subjects: Insect pests -- Control , Repellents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10427 , http://hdl.handle.net/10948/d1018273
- Description: The synthesis of p-menthane-3,8-diol via the acid-catalyzed cyclization of citronellal in a dilute aqueous sulphuric acid medium was investigated using conventional batch and continuous systems in order to develop a commercial production process for said p-menthane-3,8-diol (PMD). The batch studies conducted during the first part of this study showed that the formation of PMD from citronellal occurs via an intra-molecular Prins reaction that results in the formation of both the desired PMD product, as well as the partially hydrated isopulegol. It was shown that the formationof the by- product, PMD-acetal, results from the reaction between an intermediate, 5-methyl-2- isopropylcyclohexanol, and the citronellal starting material, and not from the reaction between PMD and citronellal as previously reported. Kinetic studies confirmed the existence of a complicated kinetic model. The formation of PMD from citronellal displayed typical pseudo first order kinetics up to conversions of 70 after which the kinetic model becomes complicated as the result of the establishment of quasi equilibrium reactions between PMD and isopulegol (dehydration of PMD and hydration of isopulegol) and between PMD the PMD-acetal, both systems being acid catalysed. The PMD-acetal formation reaction appears to be second order with respect to PMD. Scale-up studies of the batch process to 30L and 50L scales showed that it would be extremely difficult to limit the level of PMD-acetal formation below the desired level of 1 percent, even if citronellal conversions are restricted to about 50 percent. During studies conducted on a commercially availablemicro-structured organic synthesis plant (OSP) it was shown that it is possible to perform the PMD reaction as a continuous process. The results obtained showed that the use of a micro-mixer such as the caterpillar micro-mixer did not provide enough residence time in order for desirable conversions (- 40 percent) to be obtained. By combining themicro-mixer with delay-loops of different thicknesses and lengths, and using increasing reaction temperatures, it was shown that the conversion of citronellal could be improved to some extent, but compared poorly to the expected conversions for a well-stirred batch reactor. By packing selected delay loops with inert SiC particles, improved mass transfer was observed between the organic and aqueous phases as reflected in the increased conversion of citronellal. Using the observations that were made during the use of the OSP, a continuous-flow, tubular reactor system was designed and constructed. Advanced statistical techniques were used to investigate the effect of variables such as temperature, acid concentration, reactor length, flow rate and the organic to aqueous ratio on the rate and selectivity of the reaction. Mathematical models were derived for citronellal conversion, yield of PMD and yield of PMD- acetals, and used to predict the concentrations of citronellal, PMD and PMD-acetals at set experimental conditions. The results obtained showed that it was possible to obtain a product which approached desired specifications.Downstream processing of the PMD reaction mixture as it exits the reactor requires phase separation and neutralization of the acid catalyst solution, followed by further work-up to recover unreacted starting material and intermediates for recycle back to the synthesis reactor, followed by purification of crude PMD to the desired specification. The study showed that neutralization, prior or after phase separation, does not affect the selectivity of the PMD to such a great extent, but does influence the relative conversion due to extended contact of the catalyst with the organic phase after the reaction is terminated. Recovery of unreacted citronellal and isopulegol could be achieved by a simple vacuum evaporation step, which may either be carried out in a batch manner using traditional distillation equipment, or in a continuous process using wiped-film (short path) techniques. It was also shown that selective crystallization of PMD from the crude product mixture by addition of a solvent, such as heptanes or hexane proved to be the best way of achieving the desired product specification.
- Full Text:
- Date Issued: 2009
The ecophysiology of Gelidium Pristoides (Turner) Kuetzing : towards commercial cultivation
- Authors: Steyn, Paul-Pierre
- Date: 2009
- Subjects: Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10617 , http://hdl.handle.net/10948/1117 , Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Description: The ecophysiology of the red alga Gelidium pristoides (Turner) Kuetzing was investigated in an effort to establish a technique for commercial cultivation. The seaweed is of commercial importance in South Africa where it is harvested from the intertidal zone rocky shores along the coast. It is dried and exported abroad for the extraction of agar. Yields and quality could be improved by cultivation in commercial systems. However, attempts at growing the seaweed in experimental systems have all ended in failure. This study aimed to describe the conditions in which the seaweed grows naturally; and investigate its physiological response to selected physical conditions in the laboratory in order to determine suitable conditions for mariculture. Ecological studies showed that G. pristoides grew above the spring low tide water level. The upper limit of the seaweed’s vertical distribution range, as well as its abundance, was largely dependent on wave exposure. The zone normally inhabited by G. pristoides was dominated by coralline turf in sheltered areas, while the abundance of G. pristoides increased towards more exposed rocky shore sites. The seaweed occurred among species such as Pattelid limpets and barnacles, but was usually the dominant macroalga in this zone, with coralline turf and encrusting algae being the only others. Physical conditions in the part of the intertidal zone inhabited by G. pristoides were highly variable. During low tide temperatures could vary by as much as 10°C within the three hours between tidal inundation of the seaweed population, while salinity varied by up to 9 ppt, and light intensity by as much as 800 μmol m-2 s-1. During these exposure periods the seaweed suffered up to 20% moisture loss. Laboratory experiments on the seaweed’s response to these conditions indicated that it was well adapted to such fluctuations. It had a broad salinity (20 and 40 ppt), and temperature tolerance range (18 to 24°C), with an o ptimum of temperature of 21°C for photosynthesis, while there was no difference in the photosynthetic rate of the alga within the 20 to 40 ppt salinity range. The alga had a low saturating irradiance (ca. 45 – 80 μmol m-2 s-1) equipping it well for photosynthesis in turbulent environments, with high light attenuation, but poorly to unattenuated light conditions. Exposure resulted in an initial increase in photosynthetic rate followed by a gradual decrease thereafter. pH drift experiments showed that low seawater pH, and associated increased carbon dioxide availability, resulted in an increase in photosynthetic rate. This response suggests that the seaweed has a high affinity for carbon dioxide, while the reduction in photosynthetic rate in response to bicarbonate use inhibition indicates that it also has the capacity for bicarbonate use. The high affinity of Gelidium pristoides for carbon dioxide as an inorganic carbon source appears to be the primary reason for the low abundance of the alga on sheltered rocky shore areas, and also explains the failure of the alga to grow in tank or open-water mariculture systems. Exposed rocky shores have experience heavy wave action, and the resultant aeration and mixing of nearshore waters increases the availability of carbon dioxide, which is considered a limiting resource. The absence of such mixing and aeration at sheltered site makes this less suitable habitat for G. pristoides. Periodic exposure also makes high levels of atmospheric carbon dioxide available from which the seaweed benefits. The traditional mariculture systems in which attempts have been made to cultivate the seaweed failed to satisfy either of the above conditions.
- Full Text:
- Date Issued: 2009
- Authors: Steyn, Paul-Pierre
- Date: 2009
- Subjects: Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10617 , http://hdl.handle.net/10948/1117 , Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Description: The ecophysiology of the red alga Gelidium pristoides (Turner) Kuetzing was investigated in an effort to establish a technique for commercial cultivation. The seaweed is of commercial importance in South Africa where it is harvested from the intertidal zone rocky shores along the coast. It is dried and exported abroad for the extraction of agar. Yields and quality could be improved by cultivation in commercial systems. However, attempts at growing the seaweed in experimental systems have all ended in failure. This study aimed to describe the conditions in which the seaweed grows naturally; and investigate its physiological response to selected physical conditions in the laboratory in order to determine suitable conditions for mariculture. Ecological studies showed that G. pristoides grew above the spring low tide water level. The upper limit of the seaweed’s vertical distribution range, as well as its abundance, was largely dependent on wave exposure. The zone normally inhabited by G. pristoides was dominated by coralline turf in sheltered areas, while the abundance of G. pristoides increased towards more exposed rocky shore sites. The seaweed occurred among species such as Pattelid limpets and barnacles, but was usually the dominant macroalga in this zone, with coralline turf and encrusting algae being the only others. Physical conditions in the part of the intertidal zone inhabited by G. pristoides were highly variable. During low tide temperatures could vary by as much as 10°C within the three hours between tidal inundation of the seaweed population, while salinity varied by up to 9 ppt, and light intensity by as much as 800 μmol m-2 s-1. During these exposure periods the seaweed suffered up to 20% moisture loss. Laboratory experiments on the seaweed’s response to these conditions indicated that it was well adapted to such fluctuations. It had a broad salinity (20 and 40 ppt), and temperature tolerance range (18 to 24°C), with an o ptimum of temperature of 21°C for photosynthesis, while there was no difference in the photosynthetic rate of the alga within the 20 to 40 ppt salinity range. The alga had a low saturating irradiance (ca. 45 – 80 μmol m-2 s-1) equipping it well for photosynthesis in turbulent environments, with high light attenuation, but poorly to unattenuated light conditions. Exposure resulted in an initial increase in photosynthetic rate followed by a gradual decrease thereafter. pH drift experiments showed that low seawater pH, and associated increased carbon dioxide availability, resulted in an increase in photosynthetic rate. This response suggests that the seaweed has a high affinity for carbon dioxide, while the reduction in photosynthetic rate in response to bicarbonate use inhibition indicates that it also has the capacity for bicarbonate use. The high affinity of Gelidium pristoides for carbon dioxide as an inorganic carbon source appears to be the primary reason for the low abundance of the alga on sheltered rocky shore areas, and also explains the failure of the alga to grow in tank or open-water mariculture systems. Exposed rocky shores have experience heavy wave action, and the resultant aeration and mixing of nearshore waters increases the availability of carbon dioxide, which is considered a limiting resource. The absence of such mixing and aeration at sheltered site makes this less suitable habitat for G. pristoides. Periodic exposure also makes high levels of atmospheric carbon dioxide available from which the seaweed benefits. The traditional mariculture systems in which attempts have been made to cultivate the seaweed failed to satisfy either of the above conditions.
- Full Text:
- Date Issued: 2009
The invasion of pteronia incana (blue bush) along a range of gradients in the Eastern Cape Province : it's spectral chacteristics and implications for soil moisture
- Authors: Odindi, John Odhiambo
- Date: 2009
- Subjects: Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10650 , http://hdl.handle.net/10948/1052 , Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Description: Extensive areas of the Eastern Cape Province have been invaded by Pteronia incana (Blue bush), a non-palatable patchy invader shrub that is associated with soil degradation. This study sought to establish the relationship between the invasion and a range of eco-physical and land use gradients. The impact of the invader on soil moisture flux was investigated by comparing soil moisture variations under grass, bare and P. incana invaded surfaces. Field based and laboratory spectroscopy was used to validate P. incana spectral characteristics identified from multi-temporal High Resolution Imagery (HRI). A belt transect was surveyed to gain an understanding of the occurrence of the invasion across land use, isohyetic, geologic, vegetation, pedologic and altitudinal gradients. Soil moisture sensors were calibrated and installed under the respective surfaces in order to determine soil moisture trends over a period of six months. To classify the surfaces using HRI, the pixel and sub-pixel based Perpendicular Vegetation Index (PVI) and Spectral Mixture Analysis (SMA) respectively were used. There was no clear trend established between the underlying geology and P. incana invasion. Land disturbance in general was strongly associated with the invasion, as the endemic zone for the invasion mainly comprised abandoned cultivated and overgrazed land. Isohyetic gradients emerged as the major limiting factor of the invasion; a distinct zone below 619mm of mean annual rainfall was identified as the apparent boundary for the invasion. Low organic matter content identified under invaded areas was attributed to the patchy nature of the invader, leading to loss of the top soil in the bare inter-patch areas. The area covered by grass had consistently higher moisture values than P. incana and bare surfaces. The difference in post-rainfall moisture retention between grass and P. incana surfaces was significant up to about six days, after which a near parallel trend was noticed towards the ensuing rainfall episode. Whereas a higher amount of moisture was recorded on grass, the surface experienced moisture loss faster than the invaded and bare surfaces after each rainfall episode. ii There was consistency in multi-temporal Digital Number (DN) values for the surfaces investigated. The typically low P. incana reflectance in the Near Infrared band, identified from the multi-temporal HRI was validated by field and laboratory spectroscopy. The PVI showed clear spectral separability between all the land surfaces in the respective multi-temporal HRI. The consistence of the PVI with the unmixed surface image fractions from the SMA illustrates that using HRI, the effectiveness of the PVI is not impeded by the mixed pixel problem. Results of the laboratory spectroscopy that validated HRI analyses showed that P. incana’s typically low reflectance is a function of its leaf canopy, as higher proportions of leaves gave a higher reflectance. Future research directions could focus on comparisons between P. incana and typical green vegetation internal leaf structures as potential causes of spectral differences. Collection of spectra for P incana and other invader vegetation types, some of which have similar characteristics, with a view to assembling a spectral library for delineating invaded environments using imagery, is another research direction.
- Full Text:
- Date Issued: 2009
- Authors: Odindi, John Odhiambo
- Date: 2009
- Subjects: Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10650 , http://hdl.handle.net/10948/1052 , Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Description: Extensive areas of the Eastern Cape Province have been invaded by Pteronia incana (Blue bush), a non-palatable patchy invader shrub that is associated with soil degradation. This study sought to establish the relationship between the invasion and a range of eco-physical and land use gradients. The impact of the invader on soil moisture flux was investigated by comparing soil moisture variations under grass, bare and P. incana invaded surfaces. Field based and laboratory spectroscopy was used to validate P. incana spectral characteristics identified from multi-temporal High Resolution Imagery (HRI). A belt transect was surveyed to gain an understanding of the occurrence of the invasion across land use, isohyetic, geologic, vegetation, pedologic and altitudinal gradients. Soil moisture sensors were calibrated and installed under the respective surfaces in order to determine soil moisture trends over a period of six months. To classify the surfaces using HRI, the pixel and sub-pixel based Perpendicular Vegetation Index (PVI) and Spectral Mixture Analysis (SMA) respectively were used. There was no clear trend established between the underlying geology and P. incana invasion. Land disturbance in general was strongly associated with the invasion, as the endemic zone for the invasion mainly comprised abandoned cultivated and overgrazed land. Isohyetic gradients emerged as the major limiting factor of the invasion; a distinct zone below 619mm of mean annual rainfall was identified as the apparent boundary for the invasion. Low organic matter content identified under invaded areas was attributed to the patchy nature of the invader, leading to loss of the top soil in the bare inter-patch areas. The area covered by grass had consistently higher moisture values than P. incana and bare surfaces. The difference in post-rainfall moisture retention between grass and P. incana surfaces was significant up to about six days, after which a near parallel trend was noticed towards the ensuing rainfall episode. Whereas a higher amount of moisture was recorded on grass, the surface experienced moisture loss faster than the invaded and bare surfaces after each rainfall episode. ii There was consistency in multi-temporal Digital Number (DN) values for the surfaces investigated. The typically low P. incana reflectance in the Near Infrared band, identified from the multi-temporal HRI was validated by field and laboratory spectroscopy. The PVI showed clear spectral separability between all the land surfaces in the respective multi-temporal HRI. The consistence of the PVI with the unmixed surface image fractions from the SMA illustrates that using HRI, the effectiveness of the PVI is not impeded by the mixed pixel problem. Results of the laboratory spectroscopy that validated HRI analyses showed that P. incana’s typically low reflectance is a function of its leaf canopy, as higher proportions of leaves gave a higher reflectance. Future research directions could focus on comparisons between P. incana and typical green vegetation internal leaf structures as potential causes of spectral differences. Collection of spectra for P incana and other invader vegetation types, some of which have similar characteristics, with a view to assembling a spectral library for delineating invaded environments using imagery, is another research direction.
- Full Text:
- Date Issued: 2009
The selective dechlorination of poly-chlorophenols
- Authors: Thomas, Maxwell Paul
- Date: 2009
- Subjects: Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10391 , http://hdl.handle.net/10948/1124 , Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Description: Liquid phase catalytic hydrodechlorinations can provide a convenient and environmentally friendly method for treating organic chlorinated compounds in waste streams generated during the manufacturing of agrochemicals. During such treatment hydrochloric acid is generated as a by-product, which can be easily neutralized employing a base to yield an inorganic salt. This work describes the results obtained during the liquid phase hydrodechlorination of 2,6-dichlorophenol (2,6-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP). The hydrodechlorination of these chlorinated phenolic compounds in a mixture of methanol and water was investigated using supported and unsupported palladium catalysts to yield lower chlorinated phenols or phenol. Various parameters were investigated such as catalyst concentration, ammonium formate concentration, effect of base addition and effect of temperature. During this study two methods of hydrodechlorination were also investigated such as hydride-transfer hydrogenolysis, using ammonium formate, and hydrogenolysis, using dihydrogen. These methods offer a mild treatment in terms of the reaction temperature with temperatures used below 800C. A comparison of the palladium catalyst systems using these methods also showed that Pd/C produced the best results in terms of the hydrodechlorination rate and the selectivity towards phenol. When the ammonium formate method was used, complete hydrodechlorination of both substrates was achieved in 1h of reaction time at a selectivity of 100 percent towards phenol. A comparison of the method using dihydrogen and Pd/C showed that the reaction rate and the selectivity towards phenol during the hydrodechlorination of 2,6-DCP were 87.92 percent and 93.30 percent. Similarly, the reaction rate and selectivity during 2,4,6- TCP hydrodechlorination were 63.77 percent and 70.57 percent. These results were achieved in a reaction time of 3 hours. A high catalyst loading increases the reaction rate at the expense of selectivity, due to the formation of cyclohexanone, formed during further hydrogenation of phenol. The formation of cyclohexanone was limited at high temperatures (ca. 800C) with none detected during the hydrodechlorination of 2,6-DCP and 0.19 percent during the hydrodechlorination of 2,4,6-TCP. Evaluation of the hydrodechlorination parameters showed that the catalytic efficiency of the Pd/C catalysts was inhibited as the reaction proceeded due to the formation of HCl as by-product. A significant increase in the reaction rate was achieved when the reaction was performed in the presence of an inorganic base, which neutralized HCl.
- Full Text:
- Date Issued: 2009
- Authors: Thomas, Maxwell Paul
- Date: 2009
- Subjects: Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10391 , http://hdl.handle.net/10948/1124 , Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Description: Liquid phase catalytic hydrodechlorinations can provide a convenient and environmentally friendly method for treating organic chlorinated compounds in waste streams generated during the manufacturing of agrochemicals. During such treatment hydrochloric acid is generated as a by-product, which can be easily neutralized employing a base to yield an inorganic salt. This work describes the results obtained during the liquid phase hydrodechlorination of 2,6-dichlorophenol (2,6-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP). The hydrodechlorination of these chlorinated phenolic compounds in a mixture of methanol and water was investigated using supported and unsupported palladium catalysts to yield lower chlorinated phenols or phenol. Various parameters were investigated such as catalyst concentration, ammonium formate concentration, effect of base addition and effect of temperature. During this study two methods of hydrodechlorination were also investigated such as hydride-transfer hydrogenolysis, using ammonium formate, and hydrogenolysis, using dihydrogen. These methods offer a mild treatment in terms of the reaction temperature with temperatures used below 800C. A comparison of the palladium catalyst systems using these methods also showed that Pd/C produced the best results in terms of the hydrodechlorination rate and the selectivity towards phenol. When the ammonium formate method was used, complete hydrodechlorination of both substrates was achieved in 1h of reaction time at a selectivity of 100 percent towards phenol. A comparison of the method using dihydrogen and Pd/C showed that the reaction rate and the selectivity towards phenol during the hydrodechlorination of 2,6-DCP were 87.92 percent and 93.30 percent. Similarly, the reaction rate and selectivity during 2,4,6- TCP hydrodechlorination were 63.77 percent and 70.57 percent. These results were achieved in a reaction time of 3 hours. A high catalyst loading increases the reaction rate at the expense of selectivity, due to the formation of cyclohexanone, formed during further hydrogenation of phenol. The formation of cyclohexanone was limited at high temperatures (ca. 800C) with none detected during the hydrodechlorination of 2,6-DCP and 0.19 percent during the hydrodechlorination of 2,4,6-TCP. Evaluation of the hydrodechlorination parameters showed that the catalytic efficiency of the Pd/C catalysts was inhibited as the reaction proceeded due to the formation of HCl as by-product. A significant increase in the reaction rate was achieved when the reaction was performed in the presence of an inorganic base, which neutralized HCl.
- Full Text:
- Date Issued: 2009
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