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
Synthesis and characterization of novel platinum complexes : their anticancer behaviour
- Authors: Myburgh, Jolanda
- Date: 2009
- Subjects: Complex compounds -- Synthesis , Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10429 , http://hdl.handle.net/10948/d1018621
- Description: In this dissertation novel non-leaving groups were employed to synthesize platinum complexes which can contribute to the understanding or improvement of anticancer action. These complexes basically consist of (NS)-chelate and amineplatinum complexes. Bidentate (NS)-donor ligands were used as non-leaving ligands in the syntheses of platinum(II) complexes with iodide, chloride, bromide and oxalate anions as leaving groups. These complexes were synthesized and studied since many questions regarding the interaction of sulfur donors and platinum still exists. These relate to thermodynamic and kinetic factors and their influence on anticancer action. In this dissertation the properties of novel platinum(II) complexes of a bidentate ligand having an aromatic nitrogen-donor atom in combination with a thioethereal sulfur atom capable of forming a five membered ring with platinum(II) were studied. The general structure of the (NS) -ligands used were N-alkyl-2-methylthioalkyl imidazole. Alkyl groups used were methyl, ethyl and propyl. Although amine complexes of platinum have been extensively studied there are some new aspects of these that are worthwhile investigating. In this dissertation amines having planar attachments which will be at an angle with the coordination plane viz. benzylamine and amines having cyclic aliphatic groups namely cyclopropyl and cyclohexyl were investigated. Some of the (NS) - and amineplatinum(II) complexes were oxidised to their mononitroplatinum(IV) analogues . The motivation for the synthesis of these complexes was the greater kinetic stability of platinum(IV) and recent research has shown that a specific type of platinum(IV) compound shows suitable properties as an anticancer agent. These complexes were characterised by a variety of spectral means (IR, NMR, mass spectroscopy) as well as elemental analysis, solubility determinations, thermal analysis (TGA), ionization studies and finally their anticancer behaviour towards three different cell lines(Hela, MCF 7, Ht29) and in this process they were compared to the behaviour of cisplatin as a reference. A few have shown promising anticancer behaviour.
- Full Text:
- Date Issued: 2009
- Authors: Myburgh, Jolanda
- Date: 2009
- Subjects: Complex compounds -- Synthesis , Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10429 , http://hdl.handle.net/10948/d1018621
- Description: In this dissertation novel non-leaving groups were employed to synthesize platinum complexes which can contribute to the understanding or improvement of anticancer action. These complexes basically consist of (NS)-chelate and amineplatinum complexes. Bidentate (NS)-donor ligands were used as non-leaving ligands in the syntheses of platinum(II) complexes with iodide, chloride, bromide and oxalate anions as leaving groups. These complexes were synthesized and studied since many questions regarding the interaction of sulfur donors and platinum still exists. These relate to thermodynamic and kinetic factors and their influence on anticancer action. In this dissertation the properties of novel platinum(II) complexes of a bidentate ligand having an aromatic nitrogen-donor atom in combination with a thioethereal sulfur atom capable of forming a five membered ring with platinum(II) were studied. The general structure of the (NS) -ligands used were N-alkyl-2-methylthioalkyl imidazole. Alkyl groups used were methyl, ethyl and propyl. Although amine complexes of platinum have been extensively studied there are some new aspects of these that are worthwhile investigating. In this dissertation amines having planar attachments which will be at an angle with the coordination plane viz. benzylamine and amines having cyclic aliphatic groups namely cyclopropyl and cyclohexyl were investigated. Some of the (NS) - and amineplatinum(II) complexes were oxidised to their mononitroplatinum(IV) analogues . The motivation for the synthesis of these complexes was the greater kinetic stability of platinum(IV) and recent research has shown that a specific type of platinum(IV) compound shows suitable properties as an anticancer agent. These complexes were characterised by a variety of spectral means (IR, NMR, mass spectroscopy) as well as elemental analysis, solubility determinations, thermal analysis (TGA), ionization studies and finally their anticancer behaviour towards three different cell lines(Hela, MCF 7, Ht29) and in this process they were compared to the behaviour of cisplatin as a reference. A few have shown promising anticancer behaviour.
- Full Text:
- Date Issued: 2009
A Speciation study of the chloro-hydroxo complexes of Pt(II)
- Authors: Davis, John Christopher
- Date: 2009
- Subjects: Platinum , Platinum -- Separation , Platinum compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10388 , http://hdl.handle.net/10948/1213 , Platinum , Platinum -- Separation , Platinum compounds
- Description: In this study a method was developed to identify and quantify platinum(II) complexes of the type [PtCl4-n(OH)n]2- and [PtCl4-n(H2O)n]2-n. Separation of the various species was achieved with the aid of a hyphenated reversed phase HPLC-ICP-MS technique coupled with an ion-pairing reagent, HMHDCl2. The adsorption of HMHD2+ onto a C-18 column was investigated by generating a series of breakthrough curves. It was found that the selectivity for high charge density anions originates from its low surface coverage relative to TBA+, which on the other hand could not separate Pt(II) complexes. The peaks in the chromatographic traces were assigned by following the stepwise ligand substitution of [PtCl4]2- in hydroxide medium with UV/Vis spectrophotometry and HPLC-ICP-MS simultaneously. A computer program was written by the author to analyse chromatographic data by deconvoluting the chromatogram into its individual components and calculating the mole fraction of each component. The validity of the consecutive pseudo-first order model was validated by constructing 3D Mauser diagrams with the raw spectrophotometric data (A1 vs A2 vs A3). Additional software was used to simulate the raw spectrophotometric data and processed chromatographic data. The pseudo-first order rate constants obtained in both cases were in agreement with each other. Hence, peaks were assigned to [PtCl4]2-, [PtCl3(OH)]2-, [PtCl2(OH)2]2-, [PtCl3(H2O)]-. The molar extinction coefficient spectra of [PtCl3(OH)]2- and [PtCl2(OH)2]2- were obtained by simulating the spectrophotometric data at wavelengths from 280 to 450 nm. The reaction of [PtCl4]2- with sodium hydroxide was investigated with UV/Vis spectrophotometry at 25 °C. A rate constant consisting of a first and second order term was obtained. The first order term agreed with what has been reported in the literature for aquation of [PtCl4]2- at 25 degrees C. The influence of temperature was established by conducting the experiment at different temperatures. It was found that the reaction proceeds essentially via aquation at elevated temperatures.
- Full Text:
- Date Issued: 2009
- Authors: Davis, John Christopher
- Date: 2009
- Subjects: Platinum , Platinum -- Separation , Platinum compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10388 , http://hdl.handle.net/10948/1213 , Platinum , Platinum -- Separation , Platinum compounds
- Description: In this study a method was developed to identify and quantify platinum(II) complexes of the type [PtCl4-n(OH)n]2- and [PtCl4-n(H2O)n]2-n. Separation of the various species was achieved with the aid of a hyphenated reversed phase HPLC-ICP-MS technique coupled with an ion-pairing reagent, HMHDCl2. The adsorption of HMHD2+ onto a C-18 column was investigated by generating a series of breakthrough curves. It was found that the selectivity for high charge density anions originates from its low surface coverage relative to TBA+, which on the other hand could not separate Pt(II) complexes. The peaks in the chromatographic traces were assigned by following the stepwise ligand substitution of [PtCl4]2- in hydroxide medium with UV/Vis spectrophotometry and HPLC-ICP-MS simultaneously. A computer program was written by the author to analyse chromatographic data by deconvoluting the chromatogram into its individual components and calculating the mole fraction of each component. The validity of the consecutive pseudo-first order model was validated by constructing 3D Mauser diagrams with the raw spectrophotometric data (A1 vs A2 vs A3). Additional software was used to simulate the raw spectrophotometric data and processed chromatographic data. The pseudo-first order rate constants obtained in both cases were in agreement with each other. Hence, peaks were assigned to [PtCl4]2-, [PtCl3(OH)]2-, [PtCl2(OH)2]2-, [PtCl3(H2O)]-. The molar extinction coefficient spectra of [PtCl3(OH)]2- and [PtCl2(OH)2]2- were obtained by simulating the spectrophotometric data at wavelengths from 280 to 450 nm. The reaction of [PtCl4]2- with sodium hydroxide was investigated with UV/Vis spectrophotometry at 25 °C. A rate constant consisting of a first and second order term was obtained. The first order term agreed with what has been reported in the literature for aquation of [PtCl4]2- at 25 degrees C. The influence of temperature was established by conducting the experiment at different temperatures. It was found that the reaction proceeds essentially via aquation at elevated temperatures.
- Full Text:
- Date Issued: 2009
Solvent-free synthesis of bisferrocenylimines and their coordination to rhodium (I)
- Authors: Kleyi, Phumelele Eldridge
- Date: 2009
- Subjects: Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10393 , http://hdl.handle.net/10948/1053 , Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Description: Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.
- Full Text:
- Date Issued: 2009
- Authors: Kleyi, Phumelele Eldridge
- Date: 2009
- Subjects: Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10393 , http://hdl.handle.net/10948/1053 , Organic compounds -- Synthesis , Organic solvents , Solution (Chemistry) , Chemistry, Organic , Coordination compounds
- Description: Solvent-free reactions possess advantages compared to the solvent route, such as shorter reaction times, less use of energy, better yields, etc. Herein, the synthesis and characterization of bisferrocenylimines and arylbisamines are described. Reduction of the above compounds with LAH resulted in the formation of bisferrocenylamines and arylbisamines, respectively. The coordination chemistry of all the above compounds to rhodium(I) is also discussed in the prepared complexes [Rh(COD)(NN)]ClO4, where NN = bisferrocenylimines, and [Rh(COD)(NN)]BF4, where NN = bisferrocenylamines and arylbisamines. X-ray crystal structures of the complexes [Rh(COD)(NN)]ClO4 ([3.2] and [3.3]) have been obtained. Complexes of the type [Rh(COD)(NN)]BF4 were characterized with IR and UV-vis spectroscopy, cyclic voltammetry and conductometry. The catalytic activity of the complexes was also investigated: [Rh(COD)(NN)]ClO4 for the polymerization of phenylacetylene and [Rh(COD)(NN)]BF4 for the hydroformylation of styrene.
- Full Text:
- Date Issued: 2009
Efficacy of selected Kenyan medicinal plants used in the treatment and management of Type II Diabetes
- Authors: Karachi, Jacqueline
- Date: 2009
- Subjects: Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10327 , http://hdl.handle.net/10948/1049 , Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Description: In Kenya, the prevalence of diabetes is estimated at 3-10 percent of the population. These figures could be higher because most type 2 diabetics are diagnosed many years after onset. Out of this number, 15 percent are people below 30 years of age who need prompt education to avoid complications that are associated with diabetes (DMI centre, 2004). Due to inadequate or lack of proper information, most patients especially those with type 2 diabetes are diagnosed through complications. Untreated or poorly managed diabetes is now the leading cause of eye disease and kidney failure in the world. Diabetes is the largest cause of kidney failure in the developed world, and is the fourth leading cause of global death by disease in the world (IDF, 2007). At the Kenyatta National Hospital in Nairobi, Kenya, it is the leading cause of all non-accident related amputations. It is with such statistics in mind and the grim reality of poor and inadequate health services that this research is based. The wide use of selected medicinal plants for the treatment and management of diabetes warrants the further study of these plants for potential use and commercialization. The data obtained can also be invaluable for use and reference when using these plants for medicinal purposes. The medicinal plant studied in the research is widely used in Kenya by many communities and was chosen based on ethno-pharmacological references using traditional medicinal practitioners as well as patient’s recommendations. Different in vitro and in vivo assays were studied to try and elucidate the mechanisms of action as well as the organs targeted during treatment using this plant.
- Full Text:
- Date Issued: 2009
- Authors: Karachi, Jacqueline
- Date: 2009
- Subjects: Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10327 , http://hdl.handle.net/10948/1049 , Diabetes -- Alternative treatment -- Kenya , Medicinal plants -- Kenya
- Description: In Kenya, the prevalence of diabetes is estimated at 3-10 percent of the population. These figures could be higher because most type 2 diabetics are diagnosed many years after onset. Out of this number, 15 percent are people below 30 years of age who need prompt education to avoid complications that are associated with diabetes (DMI centre, 2004). Due to inadequate or lack of proper information, most patients especially those with type 2 diabetes are diagnosed through complications. Untreated or poorly managed diabetes is now the leading cause of eye disease and kidney failure in the world. Diabetes is the largest cause of kidney failure in the developed world, and is the fourth leading cause of global death by disease in the world (IDF, 2007). At the Kenyatta National Hospital in Nairobi, Kenya, it is the leading cause of all non-accident related amputations. It is with such statistics in mind and the grim reality of poor and inadequate health services that this research is based. The wide use of selected medicinal plants for the treatment and management of diabetes warrants the further study of these plants for potential use and commercialization. The data obtained can also be invaluable for use and reference when using these plants for medicinal purposes. The medicinal plant studied in the research is widely used in Kenya by many communities and was chosen based on ethno-pharmacological references using traditional medicinal practitioners as well as patient’s recommendations. Different in vitro and in vivo assays were studied to try and elucidate the mechanisms of action as well as the organs targeted during treatment using this plant.
- Full Text:
- Date Issued: 2009
Detecting changes in elephant body condition in relation to resource quality
- Authors: De Klerk, Christelle
- Date: 2009
- Subjects: Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10704 , http://hdl.handle.net/10948/939 , Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Description: Elephants, as megaherbivores, are known to have extensive impacts on vegetation, especially in enclosed areas. This raises the issue that elephants in enclosed areas may become limited by resource availability. Resource limitation is generally expressed via density dependence, but elephants, due to their slow demography, may not be affected by initial changes in resource availability. This highlights the need for a more sensitive measure of resource limitation to allow for the detection of energy stress within a population before changes in vital rates occur. This study investigated visual changes in elephant body condition in relation to resource availability in a number of Eastern Cape reserves to assess whether body condition could be used to detect life stages, as well as seasons and sites which may be resource limited. Elephant life stages were divided into energy stressed (newly weaned calves, lactating females, and old females) and non-energy stressed classes (sub-adults and non-lactating females) to determine whether energy stressed life stages were more vulnerable to resource limitation. In the AENP it was found that lactating and old females exhibited significantly poorer body condition than non-energy stressed individuals, but that weaned calves had body conditions similar to non-energy stressed individuals. Comparisons between seasons revealed that all life stages exhibited better condition in winter than summer or spring, with lactating females showing little recovery of condition over time. Seasonal body conditions were correlated with rainfall recorded in the Addo Elephant National Park. Comparisons of elephant body condition between sites (n = 6) revealed that body condition varied across sites, with poorer body condition associated with areas of higher elephant density and low rainfall during the study period. Comparisons with faecal dietary quality data both between sites and seasons indicated that body condition also responded to changes in the availability of protein and neutral detergent fibre (NDF) of plant resources, with higher protein and lower values associated with better condition. Based on condition estimates of elephants occurring in the Addo Main Camp, it was established that this population is experiencing nutritional stress, with energy stressed individuals exhibiting the lowest body conditions. This was supported by dietary quality measures. Our findings suggest that elephant body condition is a good measure for detecting resource limitation, both within populations and between seasons, and that elephant body condition respond to relatively small changes in resource conditions, thus making it an effective measure for the detection of nutritional stress. Additionally, our findings show that energy stressed individuals, particularly lactating and old females are more vulnerable to resource limitation. This demonstrates the importance of monitoring these life stages for the detection of density dependence within populations. Finally, our data suggest that threshold values of faecal dietary quality may exist at which body condition within a population begins to deteriorate, making it possible to determine the condition of a population through values obtained in faecal samples.
- Full Text:
- Date Issued: 2009
- Authors: De Klerk, Christelle
- Date: 2009
- Subjects: Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10704 , http://hdl.handle.net/10948/939 , Elephants -- Nutrition -- South Africa -- Eastern Cape , Elephants -- Habitat -- South Africa -- Eastern Cape
- Description: Elephants, as megaherbivores, are known to have extensive impacts on vegetation, especially in enclosed areas. This raises the issue that elephants in enclosed areas may become limited by resource availability. Resource limitation is generally expressed via density dependence, but elephants, due to their slow demography, may not be affected by initial changes in resource availability. This highlights the need for a more sensitive measure of resource limitation to allow for the detection of energy stress within a population before changes in vital rates occur. This study investigated visual changes in elephant body condition in relation to resource availability in a number of Eastern Cape reserves to assess whether body condition could be used to detect life stages, as well as seasons and sites which may be resource limited. Elephant life stages were divided into energy stressed (newly weaned calves, lactating females, and old females) and non-energy stressed classes (sub-adults and non-lactating females) to determine whether energy stressed life stages were more vulnerable to resource limitation. In the AENP it was found that lactating and old females exhibited significantly poorer body condition than non-energy stressed individuals, but that weaned calves had body conditions similar to non-energy stressed individuals. Comparisons between seasons revealed that all life stages exhibited better condition in winter than summer or spring, with lactating females showing little recovery of condition over time. Seasonal body conditions were correlated with rainfall recorded in the Addo Elephant National Park. Comparisons of elephant body condition between sites (n = 6) revealed that body condition varied across sites, with poorer body condition associated with areas of higher elephant density and low rainfall during the study period. Comparisons with faecal dietary quality data both between sites and seasons indicated that body condition also responded to changes in the availability of protein and neutral detergent fibre (NDF) of plant resources, with higher protein and lower values associated with better condition. Based on condition estimates of elephants occurring in the Addo Main Camp, it was established that this population is experiencing nutritional stress, with energy stressed individuals exhibiting the lowest body conditions. This was supported by dietary quality measures. Our findings suggest that elephant body condition is a good measure for detecting resource limitation, both within populations and between seasons, and that elephant body condition respond to relatively small changes in resource conditions, thus making it an effective measure for the detection of nutritional stress. Additionally, our findings show that energy stressed individuals, particularly lactating and old females are more vulnerable to resource limitation. This demonstrates the importance of monitoring these life stages for the detection of density dependence within populations. Finally, our data suggest that threshold values of faecal dietary quality may exist at which body condition within a population begins to deteriorate, making it possible to determine the condition of a population through values obtained in faecal samples.
- Full Text:
- Date Issued: 2009
A potential biological role for microcystin in photosynthesis in Microcystis Aeruginosa
- Authors: Phelan, Richard Reginald
- Date: 2009
- Subjects: Microcystis aeruginosa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10320 , http://hdl.handle.net/10948/1285 , Microcystis aeruginosa
- Description: Neither the ecological role nor the metabolic function of microcystin is known. Cellular microcystin concentrations correlate to cellular nitrogen status for a given environmental phosphorous concentration and specific growth rate. Microcystin production is enhanced when the rate of nitrogen accumulation exceeds the relative specific growth rate and/or when cellular N:C ratios exceed the Redfield ratio as a function of reduced carbon fixation, suggesting enhanced production of microcystin under carbon stress. Additionally, a strong correlation between medium phosphate and carbon fixation, and the negative correlation between medium phosphate and microcystin combined with the cellular localization of microcystin in thylakoids supports a possible role for microcystin in enhancement of photosynthesis. Batch cultures of both Microcystis aeruginosa PCC7806 and a mcyA- knockout mutant of PCC7806 were therefore cultured at different light intensities and media treatments, so as to vary cellular N:C ratios and concentrations, and sampled for analysis of microcystin concentration, cell numbers and residual medium nitrates. Inter-strain differences in photosynthetic electron transfer rates and levels were monitored using a Hansatech PEA fluorometer and compared to cellular microcystin concentrations. An enhanced survival was observed at high light, where the toxic strain survived while the nontoxic strain became chlorotic. A strong correlation (r2 = 0.907, p< 0.001, N=22) between microcystin concentration and growth rate was observed at high light conditions. No such advantage was observed at optimal or low-light conditions and media composition had no significant effect on the relationship between toxicity and survival at high light. PCC7806 showed elevated PI(abs) values compared to the mcyA knockout strain, which indicates an increased stability of PSII. A strong correlation between PI(abs) and microcystin (r = 0.88, p< 0.005, N=15) was observed for cultures grown in modified BG11 containing 25 mM under continuous illumination of 37 μmol of photons m-2.s-1. No correlation was observed between PI(abs) and microcystin for the other treatments. The toxin producer had significantly higher values for density of active reaction centers and ii quantum efficiency compared to the mutant. A decrease in F0 in the mutant suggests degradation of the phycobiliproteins, whereas PCC7806 didn’t show a significant decrease in F0 Data indicate that microcystins play a role in photosynthesis by preventing chlorosis in saturating light conditions either by enhancing the redox stability of the phycobiliproteins or PS II, thus preventing photooxidation.
- Full Text:
- Date Issued: 2009
- Authors: Phelan, Richard Reginald
- Date: 2009
- Subjects: Microcystis aeruginosa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10320 , http://hdl.handle.net/10948/1285 , Microcystis aeruginosa
- Description: Neither the ecological role nor the metabolic function of microcystin is known. Cellular microcystin concentrations correlate to cellular nitrogen status for a given environmental phosphorous concentration and specific growth rate. Microcystin production is enhanced when the rate of nitrogen accumulation exceeds the relative specific growth rate and/or when cellular N:C ratios exceed the Redfield ratio as a function of reduced carbon fixation, suggesting enhanced production of microcystin under carbon stress. Additionally, a strong correlation between medium phosphate and carbon fixation, and the negative correlation between medium phosphate and microcystin combined with the cellular localization of microcystin in thylakoids supports a possible role for microcystin in enhancement of photosynthesis. Batch cultures of both Microcystis aeruginosa PCC7806 and a mcyA- knockout mutant of PCC7806 were therefore cultured at different light intensities and media treatments, so as to vary cellular N:C ratios and concentrations, and sampled for analysis of microcystin concentration, cell numbers and residual medium nitrates. Inter-strain differences in photosynthetic electron transfer rates and levels were monitored using a Hansatech PEA fluorometer and compared to cellular microcystin concentrations. An enhanced survival was observed at high light, where the toxic strain survived while the nontoxic strain became chlorotic. A strong correlation (r2 = 0.907, p< 0.001, N=22) between microcystin concentration and growth rate was observed at high light conditions. No such advantage was observed at optimal or low-light conditions and media composition had no significant effect on the relationship between toxicity and survival at high light. PCC7806 showed elevated PI(abs) values compared to the mcyA knockout strain, which indicates an increased stability of PSII. A strong correlation between PI(abs) and microcystin (r = 0.88, p< 0.005, N=15) was observed for cultures grown in modified BG11 containing 25 mM under continuous illumination of 37 μmol of photons m-2.s-1. No correlation was observed between PI(abs) and microcystin for the other treatments. The toxin producer had significantly higher values for density of active reaction centers and ii quantum efficiency compared to the mutant. A decrease in F0 in the mutant suggests degradation of the phycobiliproteins, whereas PCC7806 didn’t show a significant decrease in F0 Data indicate that microcystins play a role in photosynthesis by preventing chlorosis in saturating light conditions either by enhancing the redox stability of the phycobiliproteins or PS II, thus preventing photooxidation.
- Full Text:
- Date Issued: 2009
The response of the red mangrove rhizophora mucronata lam, to changes in salinity, inundation and light : predictions for future climate change
- Hoppe-Speer, Sabine Clara Lisa
- Authors: Hoppe-Speer, Sabine Clara Lisa
- Date: 2009
- Subjects: Mangrove plants , Climatic changes , Red mangrove
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10616 , http://hdl.handle.net/10948/1249 , Mangrove plants , Climatic changes , Red mangrove
- Description: Mangrove forests are subjected to many environmental factors which influence species distribution, zonation patterns as well as succession. Important driving factors in these forests are salinity, water level fluctuations and available light. This study investigated the response of red mangrove (Rhizophora mucronata Lam.) seedlings to these factors in controlled laboratory experiments. Increase in salinity and prolonged inundation within estuaries are predicted impacts resulting from sea level rise due to climate change. The study investigated the effect of five salinity treatments (0, 8, 18, 35 and 45 ppt) with a semi-diurnal tidal cycle on seedling growth. In a separate experiment the effect of different inundation treatments: no inundation, 3, 6, 9 hour tidal cycles and continuous inundation (24 h) were investigated. Both morphological and physiological responses of R. mucronata seedlings were measured. There was a decrease in growth (plant height, biomass and leaf production) with increasing salinity. Seedlings in the seawater, hypersaline and no inundation treatments showed symptoms of stress, having increased leaf necrosis ("burn marks"). The highest growth occurred in the low salinity (8 ppt) treatment, but the highest photosynthetic performance and stomatal conductance occurred in the freshwater treatment (0 ppt). The typical response of stem elongation with increasing inundation was observed in the 24 hr inundation treatment. In the light and salinity combination study there were ten different treatments of five different light treatments (unshaded, 20 percent, 50 percent, 80 percent and 90 percent shade) combined with two salinity concentrations (18 and 35 ppt). In this study the seedling growth: plant height, biomass, leaf surface area and leaf production were higher in the moderate salinity (18 ppt) treatments compared to the seawater (35 ppt) treatments. Biomass in the 35 ppt experiment decreased with increasing shade as well as in the unshaded treatments. Photosynthetic performance and stomatal conductance were lower for the unshaded treatment in both 18 and 35 ppt salinity compared to all other treatments with the same salinity. This suggests that R. mucronata more shade than sun tolerant, but overall it can be concluded that the species has a broad tolerance range. The results may be relevant in mangrove rehabilitation and predicting responses to climate change. This is important as mangrove ecosystems may adapt to changing sea levels and in order to restore areas it will be necessary to choose the mangrove species which will grow best. The results may also help to increase the protection of existing mangrove habitats.
- Full Text:
- Date Issued: 2009
- Authors: Hoppe-Speer, Sabine Clara Lisa
- Date: 2009
- Subjects: Mangrove plants , Climatic changes , Red mangrove
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10616 , http://hdl.handle.net/10948/1249 , Mangrove plants , Climatic changes , Red mangrove
- Description: Mangrove forests are subjected to many environmental factors which influence species distribution, zonation patterns as well as succession. Important driving factors in these forests are salinity, water level fluctuations and available light. This study investigated the response of red mangrove (Rhizophora mucronata Lam.) seedlings to these factors in controlled laboratory experiments. Increase in salinity and prolonged inundation within estuaries are predicted impacts resulting from sea level rise due to climate change. The study investigated the effect of five salinity treatments (0, 8, 18, 35 and 45 ppt) with a semi-diurnal tidal cycle on seedling growth. In a separate experiment the effect of different inundation treatments: no inundation, 3, 6, 9 hour tidal cycles and continuous inundation (24 h) were investigated. Both morphological and physiological responses of R. mucronata seedlings were measured. There was a decrease in growth (plant height, biomass and leaf production) with increasing salinity. Seedlings in the seawater, hypersaline and no inundation treatments showed symptoms of stress, having increased leaf necrosis ("burn marks"). The highest growth occurred in the low salinity (8 ppt) treatment, but the highest photosynthetic performance and stomatal conductance occurred in the freshwater treatment (0 ppt). The typical response of stem elongation with increasing inundation was observed in the 24 hr inundation treatment. In the light and salinity combination study there were ten different treatments of five different light treatments (unshaded, 20 percent, 50 percent, 80 percent and 90 percent shade) combined with two salinity concentrations (18 and 35 ppt). In this study the seedling growth: plant height, biomass, leaf surface area and leaf production were higher in the moderate salinity (18 ppt) treatments compared to the seawater (35 ppt) treatments. Biomass in the 35 ppt experiment decreased with increasing shade as well as in the unshaded treatments. Photosynthetic performance and stomatal conductance were lower for the unshaded treatment in both 18 and 35 ppt salinity compared to all other treatments with the same salinity. This suggests that R. mucronata more shade than sun tolerant, but overall it can be concluded that the species has a broad tolerance range. The results may be relevant in mangrove rehabilitation and predicting responses to climate change. This is important as mangrove ecosystems may adapt to changing sea levels and in order to restore areas it will be necessary to choose the mangrove species which will grow best. The results may also help to increase the protection of existing mangrove habitats.
- 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
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
Statistical models for pricing weather derivatives for Port Elizabeth
- Authors: Nasila, Mark Wopicho
- Date: 2009
- Subjects: Weather derivatives -- Prices -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10567 , http://hdl.handle.net/10948/1018 , Weather derivatives -- Prices -- South Africa -- Port Elizabeth
- Description: Weather has a significant impact on business activities of many kinds. The list of economic activities subjected to the risk of the weather include: the energy producers and consumers, the industry of leisure, the insurance industry, the food industry and the agricultural industries but the primary industry, namely the energy industry, has given rise to the demand for weather derivatives and has caused the weather risk management industry to evolve actively. A derivative is a contract or security, whose payoffs depend upon the price of an underlying asset price, and is used to control the risks of naturally-arising exposures to such an asset price. Therefore weather derivatives are financial contracts with payouts that depend on weather in some form. It is a contract that provides a payoff in response to an index level based on weather phenomena (West, 2002).The underlying variable can be for example humidity, rain, snowfall, temperature, or even sunshine. The main players who take part in the weather derivatives markets industry can be grouped in to five main categories, namely: 1) End users who are also referred to as hedgers 2) Speculators 3) Market makers 4) Brokers 5) Insurance and re-insurance companies. Since the late 90’s when the first weather derivatives transactions were recorded, the underlying market has witnessed the development of a new derivative market in the United States, which is gradually expanding across Europe. However, the newly developed market for weather derivatives is not liquid in Africa and specifically South Africa mainly due to the following factors: 1) Many companies and business organisations have not yet established a hedging policy or even figured out how their businesses or industries are exposed to weather risks. 2 2) “Since many companies and industries depend on insurance companies to cover their risks, it is possible that the solutions suggested by these companies or industries looking for protection from weather risks differ according to the cover provided by these insurance organisations “(Micali, 2008). The main aim of this study is to review available statistical models for pricing derivatives, with temperature as the underlying which could enable industries, businesses and other organisations in South Africa to protect themselves against losses due to fluctuations in the weather and therefore hedge their risks.
- Full Text:
- Date Issued: 2009
- Authors: Nasila, Mark Wopicho
- Date: 2009
- Subjects: Weather derivatives -- Prices -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10567 , http://hdl.handle.net/10948/1018 , Weather derivatives -- Prices -- South Africa -- Port Elizabeth
- Description: Weather has a significant impact on business activities of many kinds. The list of economic activities subjected to the risk of the weather include: the energy producers and consumers, the industry of leisure, the insurance industry, the food industry and the agricultural industries but the primary industry, namely the energy industry, has given rise to the demand for weather derivatives and has caused the weather risk management industry to evolve actively. A derivative is a contract or security, whose payoffs depend upon the price of an underlying asset price, and is used to control the risks of naturally-arising exposures to such an asset price. Therefore weather derivatives are financial contracts with payouts that depend on weather in some form. It is a contract that provides a payoff in response to an index level based on weather phenomena (West, 2002).The underlying variable can be for example humidity, rain, snowfall, temperature, or even sunshine. The main players who take part in the weather derivatives markets industry can be grouped in to five main categories, namely: 1) End users who are also referred to as hedgers 2) Speculators 3) Market makers 4) Brokers 5) Insurance and re-insurance companies. Since the late 90’s when the first weather derivatives transactions were recorded, the underlying market has witnessed the development of a new derivative market in the United States, which is gradually expanding across Europe. However, the newly developed market for weather derivatives is not liquid in Africa and specifically South Africa mainly due to the following factors: 1) Many companies and business organisations have not yet established a hedging policy or even figured out how their businesses or industries are exposed to weather risks. 2 2) “Since many companies and industries depend on insurance companies to cover their risks, it is possible that the solutions suggested by these companies or industries looking for protection from weather risks differ according to the cover provided by these insurance organisations “(Micali, 2008). The main aim of this study is to review available statistical models for pricing derivatives, with temperature as the underlying which could enable industries, businesses and other organisations in South Africa to protect themselves against losses due to fluctuations in the weather and therefore hedge their risks.
- Full Text:
- Date Issued: 2009
The effects of a Kenyan antidiabetic plant on insulin homeostasis
- Authors: Suleiman, Khairunisa Yahya
- Date: 2009
- Subjects: Medicinal plants -- Kenya , Insulin resistance
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10326 , http://hdl.handle.net/10948/1055 , Medicinal plants -- Kenya , Insulin resistance
- Description: The metabolic disorder diabetes; is a global epidemic affecting people in developed countries and increasingly in developing countries. In two decades time, 350 million people will be diabetic at the current rate of prevalence. In a preliminary study, insulin resistant rats were treated with Prunus Africana (plant A) for 28 days. Plasma samples obtained from P. africana treated rats had increased insulin levels compared to normal and untreated insulin resistant rats (Karachi, 2009). The treatment of insulin resistant rats with P. africana also showed increased glucose uptake in rat adipose tissue (Karachi, 2009), suggesting that P. africana had anti-diabetic properties. The aim of the study was to investigate the mechanism of the anti-diabetic properties of P africana extract. Increased insulin secretion was confirmed by the increased Cpeptide concentration in plasma samples of rats treated with P. africana. In order to explain the high insulin levels, several hypothesis’ were investigated: (1) P. africana may increase insulin secretion in β cells, hence the effect of P. africana on insulin secretion by INS-1 cells was investigated; (2) P. africana may increase insulin secretion by prolonging the half-life of glucagon like peptide-1 (GLP-1) by decreasing dipeptidyl peptidase IV (DPP IV) activity; the effect of P. africana on DPP IV activity was determined spectrophotometrically, (3) P. africana may increase the half-life of insulin in the plasma by decreasing the activity of insulin degrading enzyme (IDE); the effect of P. africana on IDE in rat muscle and spleen samples was investigated. To explain the increased glucose uptake in adipose tissue observed in the previous study two parameters were investigated: (1) increased GLUT4 expression in P. africana treated rats; the effect of P. africana treatment on the expression of glucose transporter 4 (GLUT4) was determined using real-time polymerase chain reaction (RT-PCR), (2) P. africana may increase glucose utilization; the effect of P. africana on glucose utilization was determined in 3T3-L1 cells. The plant extract did not significantly increase insulin secretion by INS-1 cells in the absence of glucose. P. africana decreased DPP IV activity in rat plasma when compared to the untreated insulin resistant rats and this could be a mechanism by which insulin secretion is increased during plant treatment. P. africana decreased IDE activity (however not significantly) when compared to the untreated insulin resistant The effects of a Kenyan antidiabetic plant on insulin homeostasis KY Suleiman VII rats. P. africana appeared to have no effect on GLUT4 expression. The plant appeared to increase glucose utilization in 3T3-L1 cells in the absence of insulin suggesting that P. africana may have insulin like activity. In summary, this study indicates that P. africana is indirectly involved in inhibiting DDPIV. This in turn can increase the half life of GLP-1, which in turn can enhance the secretion of insulin. P. africana increases glucose utilization although there was no evidence that the GLUT 4 transporter has a higher expression in the plant treated rats. Further studies should be conducted to investigate the expression of GLUT1 under the same conditons.
- Full Text:
- Date Issued: 2009
- Authors: Suleiman, Khairunisa Yahya
- Date: 2009
- Subjects: Medicinal plants -- Kenya , Insulin resistance
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10326 , http://hdl.handle.net/10948/1055 , Medicinal plants -- Kenya , Insulin resistance
- Description: The metabolic disorder diabetes; is a global epidemic affecting people in developed countries and increasingly in developing countries. In two decades time, 350 million people will be diabetic at the current rate of prevalence. In a preliminary study, insulin resistant rats were treated with Prunus Africana (plant A) for 28 days. Plasma samples obtained from P. africana treated rats had increased insulin levels compared to normal and untreated insulin resistant rats (Karachi, 2009). The treatment of insulin resistant rats with P. africana also showed increased glucose uptake in rat adipose tissue (Karachi, 2009), suggesting that P. africana had anti-diabetic properties. The aim of the study was to investigate the mechanism of the anti-diabetic properties of P africana extract. Increased insulin secretion was confirmed by the increased Cpeptide concentration in plasma samples of rats treated with P. africana. In order to explain the high insulin levels, several hypothesis’ were investigated: (1) P. africana may increase insulin secretion in β cells, hence the effect of P. africana on insulin secretion by INS-1 cells was investigated; (2) P. africana may increase insulin secretion by prolonging the half-life of glucagon like peptide-1 (GLP-1) by decreasing dipeptidyl peptidase IV (DPP IV) activity; the effect of P. africana on DPP IV activity was determined spectrophotometrically, (3) P. africana may increase the half-life of insulin in the plasma by decreasing the activity of insulin degrading enzyme (IDE); the effect of P. africana on IDE in rat muscle and spleen samples was investigated. To explain the increased glucose uptake in adipose tissue observed in the previous study two parameters were investigated: (1) increased GLUT4 expression in P. africana treated rats; the effect of P. africana treatment on the expression of glucose transporter 4 (GLUT4) was determined using real-time polymerase chain reaction (RT-PCR), (2) P. africana may increase glucose utilization; the effect of P. africana on glucose utilization was determined in 3T3-L1 cells. The plant extract did not significantly increase insulin secretion by INS-1 cells in the absence of glucose. P. africana decreased DPP IV activity in rat plasma when compared to the untreated insulin resistant rats and this could be a mechanism by which insulin secretion is increased during plant treatment. P. africana decreased IDE activity (however not significantly) when compared to the untreated insulin resistant The effects of a Kenyan antidiabetic plant on insulin homeostasis KY Suleiman VII rats. P. africana appeared to have no effect on GLUT4 expression. The plant appeared to increase glucose utilization in 3T3-L1 cells in the absence of insulin suggesting that P. africana may have insulin like activity. In summary, this study indicates that P. africana is indirectly involved in inhibiting DDPIV. This in turn can increase the half life of GLP-1, which in turn can enhance the secretion of insulin. P. africana increases glucose utilization although there was no evidence that the GLUT 4 transporter has a higher expression in the plant treated rats. Further studies should be conducted to investigate the expression of GLUT1 under the same conditons.
- Full Text:
- Date Issued: 2009
Complexes of the ReO³⁺/Re(CO)₃cores with multidentate N,O-Donor chelates
- Authors: Potgieter, Kim Carey
- Date: 2009
- Subjects: Rhenium , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10387 , http://hdl.handle.net/10948/1225 , Rhenium , Schiff bases
- Description: This study investigates the coordination modes of multidentate N,O-donor ligands toward the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with 4-aminoantipyrine (H2pap) were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The X-ray crystal structures show that both complexes display a distorted octahedral geometry around the central rhenium atom, and are mirror images of each other. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The attempted synthesis of the potentially hexadentate Schiff base ligand 1,2-bis(2-{(Z)- [(2-hydroxyphenyl)imido]methyl}phenoxy)benzene from the condensation reaction of 2- (2-((2-aminophenoxy)methyl)benzyloxy)benzenamine and salicylaldehyde produced the zwitterion derivative (H2ono) of 2-{(Z)-[2-(hydroxyphenyl)imino]methyl}phenol. The tridentate Schiff bases (Z)-2-(2-aminobenzylideneamino)phenol (H3onn) and (Z)-2-(2- (methylthio)benzylideneamino)phenol (Hons) were prepared in a similar manner. The reaction of H2ono with trans-[ReOBr3(PPh3)2] surprisingly led to the isolation of the rhenium(III) complex [ReBr(PPh3)2(ono)], in which ono acts as a dianionic tridentate ligand. The reaction of H3onn with trans-[ReOBr3(PPh3)2] produced the imidorhenium(V) complex salt [ReBr(PPh3)2(onn)]Br, in which onn is coordinated as a trianionic tridentate imidoiminophenolate. The reaction of Hons with [Re(CO)5Br] led to the further decomposition of the Hons ligand, and the rhenium(I) product fac- [Re(CO)3(ons)(Hno)] (Hno = 2-aminophenol) was isolated, with ons coordinated as a monoanionic bidentate chelate (with a free SCH3 group), and Hno present as a neutral monodentate ligand with coordination through the amino nitrogen atom. Abstract Nelson Mandela Metropolitan University vi The reactions of the potentially hexadentate ligand N,N’-{ethane-1,2- diylbis[nitrilomethylidenebenzene-1,2-diyl]}bis(2-aminobenzeneimine) (H2ted) with rhenium(V) starting materials resulted in the decomposition of the H2ted molecule to give different coordinated multidentate ligands coordinated to the rhenium(V) centers. In the reaction of H2ted with trans-[ReOBr3(PPh3)2] in ethanol, the highly unusual ‘3+3’ complex cation [Re(tnn)(Htnn)]Br2 was isolated, in which tnn is coordinated as a tridentate imido-imino-amine, and Htnn is present as a tridentate monoanionic amidoimino- amine chelate (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine). With trans-[ReO2(py)4]Cl as starting material, the neutral complex [ReO(dne)] was found, in which the tetradentate chelate dne acts as a triamido-imine. The reaction of cis- [ReO2I(PPh3)2] with H2ted led to the formation of the monocationic complex salt [ReO(ane)]PF6, with ane acting as a tetradentate dianionic diamidodiimine (H2ane = N,N’-bis[(2-aminophenyl)methylidene] ethane-1,2-diamine). The seven-coordinate rhenium(III) complex cation [Re(dhp)(PPh3)2]+ (H2dhp = 2,6-bis(2- hydroxyphenyliminomethyl)pyridine) was isolated as the iodide salt from the reaction of cis-[ReO2I(PPh3)2] with H2dhp in ethanol and as the perrhenate salt from the reaction of trans-[ReOBr3(PPh3)2] with H2dhp in methanol. Both products result from a disproportionation reaction with perrhenate also being produced in the process. The complex fac-[Re(CO)3(H2dhp)Br] was prepared from [Re(CO)5Br] and H2dhp in toluene, where the H2dhp ligand acts as a neutral bidentate NN-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, to a neutral imino nitrogen, a pyridinic nitrogen and a bromide.
- Full Text:
- Date Issued: 2009
- Authors: Potgieter, Kim Carey
- Date: 2009
- Subjects: Rhenium , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10387 , http://hdl.handle.net/10948/1225 , Rhenium , Schiff bases
- Description: This study investigates the coordination modes of multidentate N,O-donor ligands toward the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with 4-aminoantipyrine (H2pap) were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The X-ray crystal structures show that both complexes display a distorted octahedral geometry around the central rhenium atom, and are mirror images of each other. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The attempted synthesis of the potentially hexadentate Schiff base ligand 1,2-bis(2-{(Z)- [(2-hydroxyphenyl)imido]methyl}phenoxy)benzene from the condensation reaction of 2- (2-((2-aminophenoxy)methyl)benzyloxy)benzenamine and salicylaldehyde produced the zwitterion derivative (H2ono) of 2-{(Z)-[2-(hydroxyphenyl)imino]methyl}phenol. The tridentate Schiff bases (Z)-2-(2-aminobenzylideneamino)phenol (H3onn) and (Z)-2-(2- (methylthio)benzylideneamino)phenol (Hons) were prepared in a similar manner. The reaction of H2ono with trans-[ReOBr3(PPh3)2] surprisingly led to the isolation of the rhenium(III) complex [ReBr(PPh3)2(ono)], in which ono acts as a dianionic tridentate ligand. The reaction of H3onn with trans-[ReOBr3(PPh3)2] produced the imidorhenium(V) complex salt [ReBr(PPh3)2(onn)]Br, in which onn is coordinated as a trianionic tridentate imidoiminophenolate. The reaction of Hons with [Re(CO)5Br] led to the further decomposition of the Hons ligand, and the rhenium(I) product fac- [Re(CO)3(ons)(Hno)] (Hno = 2-aminophenol) was isolated, with ons coordinated as a monoanionic bidentate chelate (with a free SCH3 group), and Hno present as a neutral monodentate ligand with coordination through the amino nitrogen atom. Abstract Nelson Mandela Metropolitan University vi The reactions of the potentially hexadentate ligand N,N’-{ethane-1,2- diylbis[nitrilomethylidenebenzene-1,2-diyl]}bis(2-aminobenzeneimine) (H2ted) with rhenium(V) starting materials resulted in the decomposition of the H2ted molecule to give different coordinated multidentate ligands coordinated to the rhenium(V) centers. In the reaction of H2ted with trans-[ReOBr3(PPh3)2] in ethanol, the highly unusual ‘3+3’ complex cation [Re(tnn)(Htnn)]Br2 was isolated, in which tnn is coordinated as a tridentate imido-imino-amine, and Htnn is present as a tridentate monoanionic amidoimino- amine chelate (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine). With trans-[ReO2(py)4]Cl as starting material, the neutral complex [ReO(dne)] was found, in which the tetradentate chelate dne acts as a triamido-imine. The reaction of cis- [ReO2I(PPh3)2] with H2ted led to the formation of the monocationic complex salt [ReO(ane)]PF6, with ane acting as a tetradentate dianionic diamidodiimine (H2ane = N,N’-bis[(2-aminophenyl)methylidene] ethane-1,2-diamine). The seven-coordinate rhenium(III) complex cation [Re(dhp)(PPh3)2]+ (H2dhp = 2,6-bis(2- hydroxyphenyliminomethyl)pyridine) was isolated as the iodide salt from the reaction of cis-[ReO2I(PPh3)2] with H2dhp in ethanol and as the perrhenate salt from the reaction of trans-[ReOBr3(PPh3)2] with H2dhp in methanol. Both products result from a disproportionation reaction with perrhenate also being produced in the process. The complex fac-[Re(CO)3(H2dhp)Br] was prepared from [Re(CO)5Br] and H2dhp in toluene, where the H2dhp ligand acts as a neutral bidentate NN-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, to a neutral imino nitrogen, a pyridinic nitrogen and a bromide.
- Full Text:
- Date Issued: 2009
Raman spectroscopy of ternary III-V semiconducting films
- Authors: Mashigo, Donald
- Date: 2009
- Subjects: Raman spectroscopy , Semiconductor films , Compound semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10522 , http://hdl.handle.net/10948/1011 , Raman spectroscopy , Semiconductor films , Compound semiconductors
- Description: The III-V semiconductor compounds (i.e. In Ga As x 1-x , 1 x x InAs Sb - , In Ga Sb x 1-x and Al Ga As x 1-x ) have been studied using room temperature Raman spectroscopy. X-ray diffraction has been used as a complementary characterization technique. In this study all the III-V semiconductor compounds were grown by metal organic chemical vapour deposition (MOCVD) on GaAs and GaSb substrates. The layers were studied with respect to composition, strain variation and critical thickness. Raman spectroscopy has been employed to assess the composition dependence of optical phonons in the layers. The alloy composition was varied, while the thickness was kept constant in order to investigate compositional effects. A significant frequency shift of the phonon modes were observed as the composition changed. The composition dependence of the phonon frequencies were described by linear and polynomial expressions. The results of this study were compared with previous Raman and infrared work on III-V semiconductor compounds. Strain relaxation in InGaAs and InGaSb has been investigated by Raman and X-ray diffraction. Measurements were performed on several series of layers. For each series, the thickness was varied, while keeping the composition constant. For a given composition, the layer thicknesses were such that some layers should be fully strained, some partially relaxed and some fully relaxed. The Raman peak shifts and XRD confirm that a layer grows up to the critical thickness and then releases the strain as the thickness increases. Critical layer thickness values measured in this study were compared with published data, in which various techniques had been used to estimate the critical thickness.
- Full Text:
- Date Issued: 2009
- Authors: Mashigo, Donald
- Date: 2009
- Subjects: Raman spectroscopy , Semiconductor films , Compound semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10522 , http://hdl.handle.net/10948/1011 , Raman spectroscopy , Semiconductor films , Compound semiconductors
- Description: The III-V semiconductor compounds (i.e. In Ga As x 1-x , 1 x x InAs Sb - , In Ga Sb x 1-x and Al Ga As x 1-x ) have been studied using room temperature Raman spectroscopy. X-ray diffraction has been used as a complementary characterization technique. In this study all the III-V semiconductor compounds were grown by metal organic chemical vapour deposition (MOCVD) on GaAs and GaSb substrates. The layers were studied with respect to composition, strain variation and critical thickness. Raman spectroscopy has been employed to assess the composition dependence of optical phonons in the layers. The alloy composition was varied, while the thickness was kept constant in order to investigate compositional effects. A significant frequency shift of the phonon modes were observed as the composition changed. The composition dependence of the phonon frequencies were described by linear and polynomial expressions. The results of this study were compared with previous Raman and infrared work on III-V semiconductor compounds. Strain relaxation in InGaAs and InGaSb has been investigated by Raman and X-ray diffraction. Measurements were performed on several series of layers. For each series, the thickness was varied, while keeping the composition constant. For a given composition, the layer thicknesses were such that some layers should be fully strained, some partially relaxed and some fully relaxed. The Raman peak shifts and XRD confirm that a layer grows up to the critical thickness and then releases the strain as the thickness increases. Critical layer thickness values measured in this study were compared with published data, in which various techniques had been used to estimate the critical thickness.
- 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
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
Purification and partial characterisation of cathepsin D from ostrich skeletal muscle, and its activity during meat maturation
- Authors: Krause, Jason
- Date: 2009
- Subjects: Proteolytic enzymes , Ostrich products industry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10313 , http://hdl.handle.net/10948/1461 , Proteolytic enzymes , Ostrich products industry
- Description: Cathepsin D, a muscle proteinase, participates in lysosomally mediated protein degradation in vivo. This enzyme has been proposed to play a significant role in the postmortem proteolysis process apparently associated with tenderisation. The lack of data on the postmortem characteristics of ostrich meat, especially on the ageing process and its influence on meat tenderness, called for an investigation into this process. There is no data available for purified ostrich cathepsin D, and the aim of this study was, therefore, to isolate, purify and characterise cathepsin D from ostrich skeletal muscle and subsequently investigate the possible role that it may have in the tenderisation process of meat. Cathepsin D was successfully isolated and purified from ostrich skeletal muscle using pepstatin A-agarose chromatography. The purified enzyme was composed of two subunits (14 and 29kDa). The amino acid composition as well as the N-terminal amino acid sequence of both subunits were determined. Kinetic parameters (Km and Vm), thermodynamic parameters (Ea, ∆H, ∆S and ∆G) and functional characteristics (effect of pH, temperature and various inhibitors on cathepsin D activity) were determined and are reported in this study. Ostrich muscle cathepsin D showed a pH optimum of 4 and a temperature optimum of 45°C. The activity of cathepsin D was strongly inhibited by pepstatin A and DTT. Purified ostrich cathepsin D displayed kinetic and functional properties similar to previously reported values from various species. The effect of storage on the activity of cathepsin D was investigated over a 30 day period. It was established that substantial postmortem cathepsin D activity remained throughout the storage period, to implicate cathepsin D, fulfilling a possible role in meat maturation.
- Full Text:
- Date Issued: 2009
- Authors: Krause, Jason
- Date: 2009
- Subjects: Proteolytic enzymes , Ostrich products industry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10313 , http://hdl.handle.net/10948/1461 , Proteolytic enzymes , Ostrich products industry
- Description: Cathepsin D, a muscle proteinase, participates in lysosomally mediated protein degradation in vivo. This enzyme has been proposed to play a significant role in the postmortem proteolysis process apparently associated with tenderisation. The lack of data on the postmortem characteristics of ostrich meat, especially on the ageing process and its influence on meat tenderness, called for an investigation into this process. There is no data available for purified ostrich cathepsin D, and the aim of this study was, therefore, to isolate, purify and characterise cathepsin D from ostrich skeletal muscle and subsequently investigate the possible role that it may have in the tenderisation process of meat. Cathepsin D was successfully isolated and purified from ostrich skeletal muscle using pepstatin A-agarose chromatography. The purified enzyme was composed of two subunits (14 and 29kDa). The amino acid composition as well as the N-terminal amino acid sequence of both subunits were determined. Kinetic parameters (Km and Vm), thermodynamic parameters (Ea, ∆H, ∆S and ∆G) and functional characteristics (effect of pH, temperature and various inhibitors on cathepsin D activity) were determined and are reported in this study. Ostrich muscle cathepsin D showed a pH optimum of 4 and a temperature optimum of 45°C. The activity of cathepsin D was strongly inhibited by pepstatin A and DTT. Purified ostrich cathepsin D displayed kinetic and functional properties similar to previously reported values from various species. The effect of storage on the activity of cathepsin D was investigated over a 30 day period. It was established that substantial postmortem cathepsin D activity remained throughout the storage period, to implicate cathepsin D, fulfilling a possible role in meat maturation.
- 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
A resource allocation system for invasive alien plant control on the St. Francis Conservancy
- Authors: Reeves, Brian
- Date: 2009
- Subjects: Alien plants -- Control -- South Africa , Plant invasions -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10634 , http://hdl.handle.net/10948/1073 , Alien plants -- Control -- South Africa , Plant invasions -- South Africa
- Description: Alien invasive species pose a great threat to ecosystems and human communities (Richardson & van Wilgen 2004; Hobbs & Humphries 1995). On private lands, there is a need to find institutional, administrative and scientific responses to the alien plant problem that operate beyond the scale imposed by property boundaries (Slocombe 1998; Grumbine 1994). One such response is the development and support of institutions, such as the St Francis Conservancy, that foster cross-boundary management of landscapes (Hurley et al. 2002). This study seeks to promote collective decision-making and collaborative management by private landowners through the development of a resource allocation system for the control of alien invasive plants on the St Francis Conservancy. The conservancy is located in the south-eastern lowlands of the Cape Floristic Region, between the villages of Cape St Francis and Oyster Bay, and is comprised of the properties of multiple landowners. Mutliple Criteria Decision Analysis (MCDA) and Geographical Information Systems (GIS) techniques were integrated to provide a spatially explicit resource allocation system that considered environmental, social and economic concerns. The MCDA technique selected for use was the Analytical Hierarchy Process (AHP). This technique has a record of providing robust, defensible decisions and enabled the resource allocation decision-problem to be decomposed into a hierarchy of objectives, criteria and indicators. Stakeholders participated in the development of the resource allocation system, especially through providing input into the determination of the relative importance of criteria and indicators through the assignment of weights. Various weighting scenarios were presented and these were interpreted into an ii implementation plan. The costs and effort required to clear alien plants were estimated, and obstacles facing the implementation of the plan were identified.
- Full Text:
- Date Issued: 2009
- Authors: Reeves, Brian
- Date: 2009
- Subjects: Alien plants -- Control -- South Africa , Plant invasions -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10634 , http://hdl.handle.net/10948/1073 , Alien plants -- Control -- South Africa , Plant invasions -- South Africa
- Description: Alien invasive species pose a great threat to ecosystems and human communities (Richardson & van Wilgen 2004; Hobbs & Humphries 1995). On private lands, there is a need to find institutional, administrative and scientific responses to the alien plant problem that operate beyond the scale imposed by property boundaries (Slocombe 1998; Grumbine 1994). One such response is the development and support of institutions, such as the St Francis Conservancy, that foster cross-boundary management of landscapes (Hurley et al. 2002). This study seeks to promote collective decision-making and collaborative management by private landowners through the development of a resource allocation system for the control of alien invasive plants on the St Francis Conservancy. The conservancy is located in the south-eastern lowlands of the Cape Floristic Region, between the villages of Cape St Francis and Oyster Bay, and is comprised of the properties of multiple landowners. Mutliple Criteria Decision Analysis (MCDA) and Geographical Information Systems (GIS) techniques were integrated to provide a spatially explicit resource allocation system that considered environmental, social and economic concerns. The MCDA technique selected for use was the Analytical Hierarchy Process (AHP). This technique has a record of providing robust, defensible decisions and enabled the resource allocation decision-problem to be decomposed into a hierarchy of objectives, criteria and indicators. Stakeholders participated in the development of the resource allocation system, especially through providing input into the determination of the relative importance of criteria and indicators through the assignment of weights. Various weighting scenarios were presented and these were interpreted into an ii implementation plan. The costs and effort required to clear alien plants were estimated, and obstacles facing the implementation of the plan were identified.
- 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