Development and validation of in-process control test kits for biodiesel production
- Authors: Fibi, Pumza Oscarine
- Date: 2013
- Subjects: Biodiesel fuels -- South Africa , Biomass energy -- South Africa
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10416 , http://hdl.handle.net/10948/d1012645 , Biodiesel fuels -- South Africa , Biomass energy -- South Africa
- Description: The production of biodiesel from vegetable oils is not a new technology; it has been around since the 1950’s and both the research in terms of the different feedstock that can be used and the production of biodiesel has since been gaining momentum as there needs to be a new, sustainable and domestic alternative to petroleum fuels. These petroleum fuels pose enormous threats to the environment and therefore need to be replaced as they are mostly contributing to climate change and global warming not to mention the frequent price hikes which are crippling the South African economy. Biodiesel production using vegetable oils seems to be and is the future and a law has recently been passed which sanctions the production of biofuel locally.[1] South African fuel producers will instigate obligatory blending of fossil fuel with biofuel as the country moves to encourage investment in its biofuels sector. The production of biodiesel locally and the blending of biodiesel with other petroleum products will reduce the country’s dependence on imported fuel. The already established petrochemical companies like BP, Sasol and Engine are therefore mandated to purchase these biofuels if and when the biofuels meet the required South African National Standard (SANS) 1935 requirements. This is then where the challenge comes as most of these growing biofuel companies cannot afford to purchase testing equipment.The growing companiesthen discover upon completion of the biofuel manufacturing process that their product does not meet the required standard specification. The failure translates to a financial loss as the final product can possibly not be reworked. The aim of the project is then to assist these companies who are manufacturing biofuel, by providing them with in-house biofuel process methods which will allow for early detection, should there be a need to redo a step in the process and not wait until the completion of the production process. These in-house process-testing methods will range from pH determination, titration tests which will determine the soap content and the percentage free fatty acid content, water determination, density and visual testing. It is not cost-effective for these biodiesel manufacturers to send their samples for outsource testing as evidently the results obtained would be out of specification hence the need to provide these biodiesel manufacturers with in-house analytical testing techniques that will aid in monitoring of the biodiesel production.
- Full Text:
- Date Issued: 2013
- Authors: Fibi, Pumza Oscarine
- Date: 2013
- Subjects: Biodiesel fuels -- South Africa , Biomass energy -- South Africa
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10416 , http://hdl.handle.net/10948/d1012645 , Biodiesel fuels -- South Africa , Biomass energy -- South Africa
- Description: The production of biodiesel from vegetable oils is not a new technology; it has been around since the 1950’s and both the research in terms of the different feedstock that can be used and the production of biodiesel has since been gaining momentum as there needs to be a new, sustainable and domestic alternative to petroleum fuels. These petroleum fuels pose enormous threats to the environment and therefore need to be replaced as they are mostly contributing to climate change and global warming not to mention the frequent price hikes which are crippling the South African economy. Biodiesel production using vegetable oils seems to be and is the future and a law has recently been passed which sanctions the production of biofuel locally.[1] South African fuel producers will instigate obligatory blending of fossil fuel with biofuel as the country moves to encourage investment in its biofuels sector. The production of biodiesel locally and the blending of biodiesel with other petroleum products will reduce the country’s dependence on imported fuel. The already established petrochemical companies like BP, Sasol and Engine are therefore mandated to purchase these biofuels if and when the biofuels meet the required South African National Standard (SANS) 1935 requirements. This is then where the challenge comes as most of these growing biofuel companies cannot afford to purchase testing equipment.The growing companiesthen discover upon completion of the biofuel manufacturing process that their product does not meet the required standard specification. The failure translates to a financial loss as the final product can possibly not be reworked. The aim of the project is then to assist these companies who are manufacturing biofuel, by providing them with in-house biofuel process methods which will allow for early detection, should there be a need to redo a step in the process and not wait until the completion of the production process. These in-house process-testing methods will range from pH determination, titration tests which will determine the soap content and the percentage free fatty acid content, water determination, density and visual testing. It is not cost-effective for these biodiesel manufacturers to send their samples for outsource testing as evidently the results obtained would be out of specification hence the need to provide these biodiesel manufacturers with in-house analytical testing techniques that will aid in monitoring of the biodiesel production.
- Full Text:
- Date Issued: 2013
The effect of in vitro digestion on selected biological activities of Hypoxis sobolifera corms
- Authors: Van Rooyen, Anzel
- Date: 2013
- Subjects: Potatoes -- Therapeutic use , Medicinal plants
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10344 , http://hdl.handle.net/10948/d1020058
- Description: In South Africa part of the cultural and religious beliefs of the African people is the use of traditional remedies to treat diseases. These remedies are obtained from medicinal plants (Steenkamp, 2003). One of the most frequently traded plants in the Eastern Cape is Hypoxis, commonly known as Afrika patat, or African potato. South African traditional healers instruct patients to brew the fresh Hypoxis corm as a tea and then ingest it (Steenkamp, 2006a). This prompted an investigation into the digestive stability of a traditionally prepared Hypoxis extract. The H. sobolifera extracts were digested using a simulated gastric/small intestinal digestion and their biological activity determined. The hot water H. sobolifera extract before digestion only showed cytotoxic activity against cancer cell lines at very high concentrations which are not likely to be achieved under normal ingestion circumstances. In Chang liver cells on the other hand, chronic exposure to the hot water H. sobolifera extract increased glucose uptake in amounts similar to that of metformin. On the negative side, the glucose utilization stimulation was lost due to the simulated digestion process. The significant inhibition of AGEs by hot water H. sobolifera extract (IC50 of 6.3 Ig/ml) is a very encouraging result as treatment in the management of diabetes. This activity was only slightly reduced by the in vitro digestion process. Also observed was enzyme inhibition activity by traditionally prepared H. sobolifera, with ∝-amylase being inhibited (IC50 of approximately 250 Ig/ml) and therefore preventing or limiting starch breakdown. From the DPPH results it was clear that H. sobolifera, even when digested, is a potent anti-oxidant (IC50 of 134.4 Ig/ml when undigested compared to 162.9 when digested with β-glucosidase added to stomach digestive step). HPLC and TLC experiments revealed that rooperol which has previously been thought to be the compound responsible for the anti-oxidant activity in Hypoxis extracts, was absent from the traditional extract of H. sobolifera and therefore cannot be the sole compound exhibiting anti-oxidant activity; other compounds such as phenolics may be contributing. The phenolic and flavonoid content results revealed very highconcentrations of these compounds in the traditionally prepared H. sobolifera extract. These compounds may therefore play major roles in all of the biological activities observed from treatment with Hypoxis spp. The ROS results yielded interesting and promising results. Using standard or traditionally prepared H. sobolifera extracts, activation of differentiated U937 cells with PMA was greatly enhanced by cotreatment with the extracts, while extracts on their own did not cause significant activation. Future studies should investigate this property of the extracts as a promising immune boosterThe HPLC results showed that hypoxoside was undetectable in the hot water traditional extract and the TLC anti-oxidant experiment proved that rooperol is not present in the hot water traditional extract after treatment with β-glucosidase. This indicates that neither one of the Hypoxis compounds previously believed to be responsible for the biological activities observed are present in the extract when prepared the traditional way. Therefore, the biological activities observed in this study can be attributed to other phytochemical compounds.
- Full Text:
- Date Issued: 2013
- Authors: Van Rooyen, Anzel
- Date: 2013
- Subjects: Potatoes -- Therapeutic use , Medicinal plants
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10344 , http://hdl.handle.net/10948/d1020058
- Description: In South Africa part of the cultural and religious beliefs of the African people is the use of traditional remedies to treat diseases. These remedies are obtained from medicinal plants (Steenkamp, 2003). One of the most frequently traded plants in the Eastern Cape is Hypoxis, commonly known as Afrika patat, or African potato. South African traditional healers instruct patients to brew the fresh Hypoxis corm as a tea and then ingest it (Steenkamp, 2006a). This prompted an investigation into the digestive stability of a traditionally prepared Hypoxis extract. The H. sobolifera extracts were digested using a simulated gastric/small intestinal digestion and their biological activity determined. The hot water H. sobolifera extract before digestion only showed cytotoxic activity against cancer cell lines at very high concentrations which are not likely to be achieved under normal ingestion circumstances. In Chang liver cells on the other hand, chronic exposure to the hot water H. sobolifera extract increased glucose uptake in amounts similar to that of metformin. On the negative side, the glucose utilization stimulation was lost due to the simulated digestion process. The significant inhibition of AGEs by hot water H. sobolifera extract (IC50 of 6.3 Ig/ml) is a very encouraging result as treatment in the management of diabetes. This activity was only slightly reduced by the in vitro digestion process. Also observed was enzyme inhibition activity by traditionally prepared H. sobolifera, with ∝-amylase being inhibited (IC50 of approximately 250 Ig/ml) and therefore preventing or limiting starch breakdown. From the DPPH results it was clear that H. sobolifera, even when digested, is a potent anti-oxidant (IC50 of 134.4 Ig/ml when undigested compared to 162.9 when digested with β-glucosidase added to stomach digestive step). HPLC and TLC experiments revealed that rooperol which has previously been thought to be the compound responsible for the anti-oxidant activity in Hypoxis extracts, was absent from the traditional extract of H. sobolifera and therefore cannot be the sole compound exhibiting anti-oxidant activity; other compounds such as phenolics may be contributing. The phenolic and flavonoid content results revealed very highconcentrations of these compounds in the traditionally prepared H. sobolifera extract. These compounds may therefore play major roles in all of the biological activities observed from treatment with Hypoxis spp. The ROS results yielded interesting and promising results. Using standard or traditionally prepared H. sobolifera extracts, activation of differentiated U937 cells with PMA was greatly enhanced by cotreatment with the extracts, while extracts on their own did not cause significant activation. Future studies should investigate this property of the extracts as a promising immune boosterThe HPLC results showed that hypoxoside was undetectable in the hot water traditional extract and the TLC anti-oxidant experiment proved that rooperol is not present in the hot water traditional extract after treatment with β-glucosidase. This indicates that neither one of the Hypoxis compounds previously believed to be responsible for the biological activities observed are present in the extract when prepared the traditional way. Therefore, the biological activities observed in this study can be attributed to other phytochemical compounds.
- Full Text:
- Date Issued: 2013
The fitting of statistical distributions to wind data in coastal areas of South Africa
- Authors: Moodley, Kirshnee
- Date: 2013
- Subjects: Winds -- South Africa -- Port Elizabeth -- Speed -- Measurement , Wind power -- South Africa -- Port Elizabeth , Winds -- South Africa -- Port Elizabeth -- Measurement -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10584
- Description: Coastal South African cities like Port Elizabeth are said to have a strong potential for wind energy. This study aims to model wind data in order to be able assess the power potential belonging to a given site. The main challenge in modelling wind direction data is that it is categorized as circular data and therefore requires special techniques for handling that are different from usual statistical samples. Statistical tools such as descriptive measures and distribution fitting, were re-invented for directional data by researchers in this field. The von Mises distribution is a predominant distribution in circular statistics and is commonly used to describe wind directions. In this study, the circular principles described by previous researchers were developed by using the statistical software, Mathematica. Graphical methods to present the wind data were developed to give an overview of the behaviour of the winds in any given area. Data collected at Coega, an area near Port Elizabeth, South Africa, was used to illustrate the models which were established in this study. Circular distributions were fit to the directional data in order to make appropriate conclusions about the prevailing wind directions in this area.
- Full Text:
- Date Issued: 2013
- Authors: Moodley, Kirshnee
- Date: 2013
- Subjects: Winds -- South Africa -- Port Elizabeth -- Speed -- Measurement , Wind power -- South Africa -- Port Elizabeth , Winds -- South Africa -- Port Elizabeth -- Measurement -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10584
- Description: Coastal South African cities like Port Elizabeth are said to have a strong potential for wind energy. This study aims to model wind data in order to be able assess the power potential belonging to a given site. The main challenge in modelling wind direction data is that it is categorized as circular data and therefore requires special techniques for handling that are different from usual statistical samples. Statistical tools such as descriptive measures and distribution fitting, were re-invented for directional data by researchers in this field. The von Mises distribution is a predominant distribution in circular statistics and is commonly used to describe wind directions. In this study, the circular principles described by previous researchers were developed by using the statistical software, Mathematica. Graphical methods to present the wind data were developed to give an overview of the behaviour of the winds in any given area. Data collected at Coega, an area near Port Elizabeth, South Africa, was used to illustrate the models which were established in this study. Circular distributions were fit to the directional data in order to make appropriate conclusions about the prevailing wind directions in this area.
- Full Text:
- Date Issued: 2013
The diet of the Subantarctic (A. Tropicalis) and Antarctic (A. Gazella) Fur seal at Marion Island
- Mgibantaka, Nonkoliso Felicia
- Authors: Mgibantaka, Nonkoliso Felicia
- Date: 2013
- Subjects: Southern fur seals -- Feeding and feeds -- Antarctica , Seals (Animals) -- Antarctica , Marine ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10729 , http://hdl.handle.net/10948/d1021104
- Description: Studying the diet of marine top predators is important for understanding the trophic ecology of the predators but also the distribution, abundance and seasonal variation of prey species. Dietary studies on subantarctic fur seals (Arctocephalus tropicalis) and Antarctic fur seals (A. gazella) is important for assessing their role as predators in the Southern Ocean. Seven hundred and sixty four scats were collected from an A. tropicalis colony at Cape Davis while 659 scats were collected from an A. gazella colony at Watertunnel stream from April 2006 to March 2010. Hard remains such as fish otoliths and cephalopod beaks were used for identification and quantification of prey. A. tropicalis diet comprised of three animal groups (fish, cephalopod and crustaceans) while A. gazella diet was made up of four animal groups (fish, cephalopods, crustaceans and seabirds). Fish contributed substantially more than other prey items in the diet of both fur seal species over the study period. Both species fed predominantly on fish of the family Myctophidae which constituted a numerical abundance of 98.9 percent in scats for both species combined. A. tropicalis fed on fish prey species from eight families, namely: Myctophidae, Notosudidae, Paralepididae, Nototheniidae, Bathylagidae, Chlorophthalmidae, Sternoptychidae and Photichthyidae while A. gazella fed on fish from six of these families, with Chlorophthalmidae and Photichthyidae not represented in its diet. Cephalopods and crustaceans were found in low numbers in the diet of both seal species and seabird remains were only found in the diet of A. gazella. Numerically, the most dominant species were from the genus Gymnoscopelus followed by Protomyctophum and then Electrona. In the diet of A. tropicalis, Gymnoscopelus contributed 66 percent, Protomyctophum 18 percent and Electrona 5.9 percent while in the diet of A. gazella Gymnoscopelus, Protomyctophum and Electrona contributed 59.43 percent, 20.24 percent and 14.24 percent respectively. Gymnoscopelus species comprised G. piabilis, G. bolini, G. braueri, G. fraseri, and G. nicholsi; Protomyctophum comprised Protomyctophum bolini, P. choriodon and P. tenisoni while Electrona comprised Electrona antarctica, E. carlsbergi and E. subaspera. Gymnoscopelus piabilis was the most dominant species from this genus while Electrona carlsbergi and Protomyctophum tenisoni dominated the genus Electrona and Protomyctophum respectively. The total number of fish species utilised by A. tropicalis was twenty four while twenty three fish species were identified in A. gazella diet. Bathysauropsis gracilis only featured in the diet of A. tropicalis while Lampanyctus ater and Lepidonotothen larseni were only found in the diet of A. gazella. To compare the diet of the seal species between seasons, a year was divided into three seasons, early summer, late summer and winter. Their diet was also compared between years from 2006 to 2010. Myctophid fish species showed substantial seasonal and annual fluctuations in the diet of the two fur seal species. E. carlsbergi, G. nicholsi and G. piabilis increased in numerical abundance in winter while Melectrona ventralis increased in late summer. The numerical abundance of G. fraseri and P. tenisoni increased in early summer. Generally, the two fur seal species fed on the same prey species. However, there was a significant difference when the diet of both fur seals was compared seasonally. There was no significant difference when the diet of A. gazella was compared annually, although such a difference was apparent for A. tropicalis.
- Full Text:
- Date Issued: 2013
- Authors: Mgibantaka, Nonkoliso Felicia
- Date: 2013
- Subjects: Southern fur seals -- Feeding and feeds -- Antarctica , Seals (Animals) -- Antarctica , Marine ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10729 , http://hdl.handle.net/10948/d1021104
- Description: Studying the diet of marine top predators is important for understanding the trophic ecology of the predators but also the distribution, abundance and seasonal variation of prey species. Dietary studies on subantarctic fur seals (Arctocephalus tropicalis) and Antarctic fur seals (A. gazella) is important for assessing their role as predators in the Southern Ocean. Seven hundred and sixty four scats were collected from an A. tropicalis colony at Cape Davis while 659 scats were collected from an A. gazella colony at Watertunnel stream from April 2006 to March 2010. Hard remains such as fish otoliths and cephalopod beaks were used for identification and quantification of prey. A. tropicalis diet comprised of three animal groups (fish, cephalopod and crustaceans) while A. gazella diet was made up of four animal groups (fish, cephalopods, crustaceans and seabirds). Fish contributed substantially more than other prey items in the diet of both fur seal species over the study period. Both species fed predominantly on fish of the family Myctophidae which constituted a numerical abundance of 98.9 percent in scats for both species combined. A. tropicalis fed on fish prey species from eight families, namely: Myctophidae, Notosudidae, Paralepididae, Nototheniidae, Bathylagidae, Chlorophthalmidae, Sternoptychidae and Photichthyidae while A. gazella fed on fish from six of these families, with Chlorophthalmidae and Photichthyidae not represented in its diet. Cephalopods and crustaceans were found in low numbers in the diet of both seal species and seabird remains were only found in the diet of A. gazella. Numerically, the most dominant species were from the genus Gymnoscopelus followed by Protomyctophum and then Electrona. In the diet of A. tropicalis, Gymnoscopelus contributed 66 percent, Protomyctophum 18 percent and Electrona 5.9 percent while in the diet of A. gazella Gymnoscopelus, Protomyctophum and Electrona contributed 59.43 percent, 20.24 percent and 14.24 percent respectively. Gymnoscopelus species comprised G. piabilis, G. bolini, G. braueri, G. fraseri, and G. nicholsi; Protomyctophum comprised Protomyctophum bolini, P. choriodon and P. tenisoni while Electrona comprised Electrona antarctica, E. carlsbergi and E. subaspera. Gymnoscopelus piabilis was the most dominant species from this genus while Electrona carlsbergi and Protomyctophum tenisoni dominated the genus Electrona and Protomyctophum respectively. The total number of fish species utilised by A. tropicalis was twenty four while twenty three fish species were identified in A. gazella diet. Bathysauropsis gracilis only featured in the diet of A. tropicalis while Lampanyctus ater and Lepidonotothen larseni were only found in the diet of A. gazella. To compare the diet of the seal species between seasons, a year was divided into three seasons, early summer, late summer and winter. Their diet was also compared between years from 2006 to 2010. Myctophid fish species showed substantial seasonal and annual fluctuations in the diet of the two fur seal species. E. carlsbergi, G. nicholsi and G. piabilis increased in numerical abundance in winter while Melectrona ventralis increased in late summer. The numerical abundance of G. fraseri and P. tenisoni increased in early summer. Generally, the two fur seal species fed on the same prey species. However, there was a significant difference when the diet of both fur seals was compared seasonally. There was no significant difference when the diet of A. gazella was compared annually, although such a difference was apparent for A. tropicalis.
- Full Text:
- Date Issued: 2013
The medicinal plant Sutherlandia Frutescens regulates gene expression to reverse insulin resistace in rats
- Authors: Fortuin, Melissa
- Date: 2013
- Subjects: Insulin resistance , Medicinal plants , Genetic regulation , Insulin resistance -- Animal models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10349 , http://hdl.handle.net/10948/d1020823
- Description: Obesity can lead to Type 2 Diabetes, both conditions increase in association with physical inactivity and high-energy diets, resulting in elevated blood glucose, decreased insulin sensitivity and increased insulin resistance. Sutherlandia frutescens (S.frutescens), an anti-diabetic plant, reverses and prevents insulin resistance in a rat model and human cell culture model. Gene expression analysis in hepatocyte cultures, identified genes down regulated in insulin resistance and up regulated by S.frutescens. These included genes encoding vesicle transporter proteins, hypothesised to be linked to hepatic lipid accumulation and lipid droplet formation during insulin resistance. The aim of this study was to investigate critical genes involved in lipid droplet formation, vesicle assembly and transport in high fat diet (HFD)-induced insulin resistant rat liver tissue during the development of insulin resistance and the reversal of these changes by S.frutescens. Rats were fed a low fat diet (LFD) or HFD supplemented with S.frutescens for 2, 4 and 8 weeks. Rats fed a HFD for 12 weeks developed insulin resistance, confirmed by plasma glucose and insulin levels (compared to normal controls). Groups of these rats were gavaged with S. frutescens (50mg/kg BW), Metformin (13mg/kg BW) or water for a further 4 weeks and starved for 12 hours, anaesthetized and blood removed by heart puncture. Liver was stored in RNA-Later™ for qRT-PCR and snap-frozen in liquid nitrogen for western blotting and confocal microscopy analysis. Changes in expression of vesicle transporter genes VAMP3 and NSF were analysed by qRT-PCR and changes in the protein expression by western blotting analysis. Proteins were localised within the liver by confocal immunohistochemistry using ZEN lite™ software. Statistical analysis was performed using One-Way ANOVA and unpaired t-test. mRNA gene expression of vesicle transport components VAMP3, NSF and SNAP25 showed relatively moderate changes with considerable individual variation within control or experimental groups. Uncorrelated changes in mRNA and protein products were found and may be due to differential regulation by siRNA. Proteins also showed altered staining patterns in high fat diet rats that reverted towards normal on S. frutescens treatment, potentially reflecting functional changes associated with transport of lipid-filled vesicles.
- Full Text:
- Date Issued: 2013
- Authors: Fortuin, Melissa
- Date: 2013
- Subjects: Insulin resistance , Medicinal plants , Genetic regulation , Insulin resistance -- Animal models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10349 , http://hdl.handle.net/10948/d1020823
- Description: Obesity can lead to Type 2 Diabetes, both conditions increase in association with physical inactivity and high-energy diets, resulting in elevated blood glucose, decreased insulin sensitivity and increased insulin resistance. Sutherlandia frutescens (S.frutescens), an anti-diabetic plant, reverses and prevents insulin resistance in a rat model and human cell culture model. Gene expression analysis in hepatocyte cultures, identified genes down regulated in insulin resistance and up regulated by S.frutescens. These included genes encoding vesicle transporter proteins, hypothesised to be linked to hepatic lipid accumulation and lipid droplet formation during insulin resistance. The aim of this study was to investigate critical genes involved in lipid droplet formation, vesicle assembly and transport in high fat diet (HFD)-induced insulin resistant rat liver tissue during the development of insulin resistance and the reversal of these changes by S.frutescens. Rats were fed a low fat diet (LFD) or HFD supplemented with S.frutescens for 2, 4 and 8 weeks. Rats fed a HFD for 12 weeks developed insulin resistance, confirmed by plasma glucose and insulin levels (compared to normal controls). Groups of these rats were gavaged with S. frutescens (50mg/kg BW), Metformin (13mg/kg BW) or water for a further 4 weeks and starved for 12 hours, anaesthetized and blood removed by heart puncture. Liver was stored in RNA-Later™ for qRT-PCR and snap-frozen in liquid nitrogen for western blotting and confocal microscopy analysis. Changes in expression of vesicle transporter genes VAMP3 and NSF were analysed by qRT-PCR and changes in the protein expression by western blotting analysis. Proteins were localised within the liver by confocal immunohistochemistry using ZEN lite™ software. Statistical analysis was performed using One-Way ANOVA and unpaired t-test. mRNA gene expression of vesicle transport components VAMP3, NSF and SNAP25 showed relatively moderate changes with considerable individual variation within control or experimental groups. Uncorrelated changes in mRNA and protein products were found and may be due to differential regulation by siRNA. Proteins also showed altered staining patterns in high fat diet rats that reverted towards normal on S. frutescens treatment, potentially reflecting functional changes associated with transport of lipid-filled vesicles.
- Full Text:
- Date Issued: 2013
Isocyanide complexes of rhenium
- Authors: Schoultz, Xandri
- Date: 2013
- Subjects: Isocyanides , Rhenium , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10360 , http://hdl.handle.net/10948/d1021069
- Description: This study investigates the synthesis of rhenium(III)-isocyanide complexes with potentially bidentate ligands, as well as the reactivity of isocyanide ligands toward rhenium(I) and (V). The crystal structures of all the complexes have been determined by X-ray diffraction methods. The coordination behaviour of trans-[ReIIICl3(t-BuNC)(PPh3)2] with aniline and its derivatives were investigated. The isocyanide-containing rhenium(V) complexes [ReCl3(t-BuNC)(L)(PPh3)] were isolated, with the ligands H2L (aniline, o-phenylenediamine and anthranilic acid). In all these complexes the dianionic ligands L are coordinated monodentately as the imide. However, with 2-aminophenol the complexes [ReVCl2(t-BuNC)(L)(PPh3)2](ReO4) and [ReIIICl2(t-BuNC)(ibq)(PPh3)2] (ibq- = 2-iminobenzoquinonate) were identified as the products. [ReCl2(t-BuNC)(L)(PPh3)2](ReO4) is the product of a disproportionation reaction from Re(III) to Re(VII) and Re(V). All the above complexes show a distorted octahedral geometry around the rhenium. The products of the reaction of the Re(I) complex [Re(CO)5Cl] with isocyanides (tert-butyl- and cyclohexylisocyanide) are reported. Rhenium(I) tricarbonyl complexes of the form [Re(CO)3(CNR)2Cl] were isolated and they were characterized structurally and spectroscopically. The tricarbonyls are coordinated in the typical facial-fashion, whereas the isocyanides are coordinated cis to each other. The reaction of [Re(CO)3(t-BuNC)2Cl] with H2O led to the formation of the rhenium(I) complex [Re(CO)3(t-BuNC)2(OH2)] in which the aquo ligand can readily be substituted by a more complex ligand. The reaction of the rhenium(V) complexes cis-[ReO2I(PPh3)2] and mer-[ReOCl3(SMe2)(OPPh3)] with isocyanides were studied. The seven-coordinate trigonal prismatic, square faced monocapped rhenium(III) complex [ReI3(t-BuNC)3(PPh3)] was surprisingly isolated upon reacting cis-[ReO2I(PPh3)2] with tert-butyl isocyanide. The dimeric complex (μ-O)[ReOCl2(CNC6H11)2]2 was obtained from the reaction of mer-[ReOCl3(SMe2)(OPPh3)] with cyclohexyl isocyanide.
- Full Text:
- Date Issued: 2013
- Authors: Schoultz, Xandri
- Date: 2013
- Subjects: Isocyanides , Rhenium , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10360 , http://hdl.handle.net/10948/d1021069
- Description: This study investigates the synthesis of rhenium(III)-isocyanide complexes with potentially bidentate ligands, as well as the reactivity of isocyanide ligands toward rhenium(I) and (V). The crystal structures of all the complexes have been determined by X-ray diffraction methods. The coordination behaviour of trans-[ReIIICl3(t-BuNC)(PPh3)2] with aniline and its derivatives were investigated. The isocyanide-containing rhenium(V) complexes [ReCl3(t-BuNC)(L)(PPh3)] were isolated, with the ligands H2L (aniline, o-phenylenediamine and anthranilic acid). In all these complexes the dianionic ligands L are coordinated monodentately as the imide. However, with 2-aminophenol the complexes [ReVCl2(t-BuNC)(L)(PPh3)2](ReO4) and [ReIIICl2(t-BuNC)(ibq)(PPh3)2] (ibq- = 2-iminobenzoquinonate) were identified as the products. [ReCl2(t-BuNC)(L)(PPh3)2](ReO4) is the product of a disproportionation reaction from Re(III) to Re(VII) and Re(V). All the above complexes show a distorted octahedral geometry around the rhenium. The products of the reaction of the Re(I) complex [Re(CO)5Cl] with isocyanides (tert-butyl- and cyclohexylisocyanide) are reported. Rhenium(I) tricarbonyl complexes of the form [Re(CO)3(CNR)2Cl] were isolated and they were characterized structurally and spectroscopically. The tricarbonyls are coordinated in the typical facial-fashion, whereas the isocyanides are coordinated cis to each other. The reaction of [Re(CO)3(t-BuNC)2Cl] with H2O led to the formation of the rhenium(I) complex [Re(CO)3(t-BuNC)2(OH2)] in which the aquo ligand can readily be substituted by a more complex ligand. The reaction of the rhenium(V) complexes cis-[ReO2I(PPh3)2] and mer-[ReOCl3(SMe2)(OPPh3)] with isocyanides were studied. The seven-coordinate trigonal prismatic, square faced monocapped rhenium(III) complex [ReI3(t-BuNC)3(PPh3)] was surprisingly isolated upon reacting cis-[ReO2I(PPh3)2] with tert-butyl isocyanide. The dimeric complex (μ-O)[ReOCl2(CNC6H11)2]2 was obtained from the reaction of mer-[ReOCl3(SMe2)(OPPh3)] with cyclohexyl isocyanide.
- Full Text:
- Date Issued: 2013
Propagating some commonly-used South African medicinal plants with compost and vermitea
- Authors: Faulconbridge, Steven Craig
- Date: 2013
- Subjects: Medicinal plants -- Propagation -- South Africa , Compost -- South Africa
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10736 , http://hdl.handle.net/10948/d1020316
- Description: The use of many of South Africa’s medicinal plants has shown marked increase with over 27 million users in South Africa alone. Most plants are still being unsustainably wild-harvested, a major concern for biodiversity conservation. Commercial interest in certain more commonly-used species has increased, with potential to cultivate medicinal plants on a more sustainable basis. Focus has shifted from conventional use of synthetic fertilisers, pesticides and fungicides to more organic methods of plant propagation. Aqueous extract derived from earthworm composted food waste (vermitea) was used to study the germination and rooting success of selected species. Also survival and growth performance of selected plants grown in a medium amended with commercial NPK fertiliser was compared to those grown in the same medium amended with compost and to those grown in the same medium amended with compost with weekly applications of vermitea. No change in germination success was noted. Vermitea showed promising results on the rooting of cuttings. The application of NPK improved growth performance (biomass) significantly for all species tested. However, they had lower root:shoot ratios as well as lower survival rates compared to plants under the compost and compost/vermitea treatments. The improved survival of these plants highlights the potential of these organic treatments on the propagation of selected medicinal plants.
- Full Text:
- Date Issued: 2013
- Authors: Faulconbridge, Steven Craig
- Date: 2013
- Subjects: Medicinal plants -- Propagation -- South Africa , Compost -- South Africa
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10736 , http://hdl.handle.net/10948/d1020316
- Description: The use of many of South Africa’s medicinal plants has shown marked increase with over 27 million users in South Africa alone. Most plants are still being unsustainably wild-harvested, a major concern for biodiversity conservation. Commercial interest in certain more commonly-used species has increased, with potential to cultivate medicinal plants on a more sustainable basis. Focus has shifted from conventional use of synthetic fertilisers, pesticides and fungicides to more organic methods of plant propagation. Aqueous extract derived from earthworm composted food waste (vermitea) was used to study the germination and rooting success of selected species. Also survival and growth performance of selected plants grown in a medium amended with commercial NPK fertiliser was compared to those grown in the same medium amended with compost and to those grown in the same medium amended with compost with weekly applications of vermitea. No change in germination success was noted. Vermitea showed promising results on the rooting of cuttings. The application of NPK improved growth performance (biomass) significantly for all species tested. However, they had lower root:shoot ratios as well as lower survival rates compared to plants under the compost and compost/vermitea treatments. The improved survival of these plants highlights the potential of these organic treatments on the propagation of selected medicinal plants.
- Full Text:
- Date Issued: 2013
Reactions towards the synthesis of the uncommon P57 cymarose moiety
- Authors: Mahanjana, Lungelwa
- Date: 2013
- Subjects: Chemistry, Organic , Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/6711 , vital:21136
- Description: The work described in this study aims to investigate methods that will improve a lengthy synthetic pathway in the synthesis of the P57 cymarose moiety, and to examine the conformational structure of certain glycosides in order to shed light on the problematic stereochemical issues surrounding the formation of the cymarose glycosyl donor. The cymarose moiety forms part of the trisaccharide derivative present in P57, an appetite suppressant molecule. Modification of reaction steps in the conversion of the stereochemistry at C-3 of a previously reported synthesis of the P57 cymarose moiety was carried out. The first step was the selective oxidation of D-glucal using Pd/C in the presence of acetonitrile. These reaction conditions are more appropriate for the oxidation step to avoid decomposition of the formed molecules. Successive protection of the free OH groups was followed by NaBH4 reduction under stereo-controlled conditions, influenced by CeCl3•7H2O. However, the reduced product could not be isolated from the starting material and this led to ambiguous results when attempting to confirm whether the conversion of the stereochemistry at C-3 had occurred or not. The effect of reaction conditions, such as change in reaction temperature, during the preparation of the cymarose glycosyl donor was studied in order to find suitable reaction conditions to produce α,β-allo derivatives with high stereoselectivity. Compared to the reported synthetic method, this set-up gave improved yields with, unfortunately, similar or slightly lower selectivity to the formation of α-altro:α,β-allo derivative. Examination of the conformational structure of the allal derivative, in order to understand the mechanism at work during the placement of the directing group at C-2, was carried out using molecular modelling. The mechanistic implications of this very short study are discussed and it provides some insights into the likely pathway of the iodination reaction and its selectivity in particular, to the D-allose system.
- Full Text:
- Date Issued: 2013
- Authors: Mahanjana, Lungelwa
- Date: 2013
- Subjects: Chemistry, Organic , Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/6711 , vital:21136
- Description: The work described in this study aims to investigate methods that will improve a lengthy synthetic pathway in the synthesis of the P57 cymarose moiety, and to examine the conformational structure of certain glycosides in order to shed light on the problematic stereochemical issues surrounding the formation of the cymarose glycosyl donor. The cymarose moiety forms part of the trisaccharide derivative present in P57, an appetite suppressant molecule. Modification of reaction steps in the conversion of the stereochemistry at C-3 of a previously reported synthesis of the P57 cymarose moiety was carried out. The first step was the selective oxidation of D-glucal using Pd/C in the presence of acetonitrile. These reaction conditions are more appropriate for the oxidation step to avoid decomposition of the formed molecules. Successive protection of the free OH groups was followed by NaBH4 reduction under stereo-controlled conditions, influenced by CeCl3•7H2O. However, the reduced product could not be isolated from the starting material and this led to ambiguous results when attempting to confirm whether the conversion of the stereochemistry at C-3 had occurred or not. The effect of reaction conditions, such as change in reaction temperature, during the preparation of the cymarose glycosyl donor was studied in order to find suitable reaction conditions to produce α,β-allo derivatives with high stereoselectivity. Compared to the reported synthetic method, this set-up gave improved yields with, unfortunately, similar or slightly lower selectivity to the formation of α-altro:α,β-allo derivative. Examination of the conformational structure of the allal derivative, in order to understand the mechanism at work during the placement of the directing group at C-2, was carried out using molecular modelling. The mechanistic implications of this very short study are discussed and it provides some insights into the likely pathway of the iodination reaction and its selectivity in particular, to the D-allose system.
- Full Text:
- Date Issued: 2013
Technology transfer of antibacterial oral solid dosage form in a pharmaceutical industry
- Authors: Ramloll, Jason
- Date: 2013
- Subjects: Clinical pharmacology Pharmacy -- Research , Pharmaceutical industry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47913 , vital:40398
- Description: Technology transfer (TT) looks at the transfer of intellectual property from one manufacturing site to another. If carried out successfully, a TT can increase the leveraging capability of the company acquiring the intellectual property together with its brand strength. This in turn aids in a decreased time to market of the final dosage form produced. The aim of the research was to assess the TT of an antibacterial oral solid dosage form from one manufacturing site to another. An expected change of manufacturing equipment from a single-pot to a multi-phase system took place due to the equipment available at the receiving unit. The assessment done by the researcher was performed in the capacity of an observer. The assessment of the TT was performed by observing the critical stages during the transfer process, namely the development and validation stages. Prior to the start of the development stage, a characterisation of innovator was performed. At this stage, innovator batches received from the Sending Unit (SU) were characterised to allow for a means of comparison. The development stage allows for the determination of the robustness of the formulation to be used whilst the validation stage will look at the reproducibility of the chosen formulation. During the development stage, small scale trials were manufactured with amendments made to the original formulation. The amendments allowed for a formulation more comparable to the innovator product with regards to its dissolution profile. The comparable batch produced at a small scale was then up-scaled to a production scale batch and these were compared to the innovator products. The amendments made were on the amount of granulation fluid and binder as well as the method of addition of the disintegrant. When a large scale batch comparable to that of the innovator product was produced, the validation stage was started. With the aim of showing reproducibility of the Receiving Unit (RU) at producing large scale batches, three batches were produced. These were tested for all critical parameters, namely through the loss on drying, particle size distribution, hardness, disintegration and dissolution tests and, the results of the tests were compared to the specifications set by the SU. They were also compared to each other, enabling statistical determination of any significant difference across the batches through the use of comparative statistical analyses. Comparison of batches, at the development and validation stage, was done using the dissolution potential of the batches. These were performed through the use of statistical analyses. The RU made use of the similarity factor (F2) to compare the dissolution profiles. For the purpose of this research, the 1-Way analysis of variance was also used, which compared to the similarity factor, took in consideration the level of variance of the batches produced. Results and discussion: During the development stage amendments were made to produce a batch comparable to the innovator product. The amendments that led to the production of a comparable batch consisted of an extra 14 % of granulation fluid as well as 50 % of the disintegrant being added intra-granularly with the other 50 % added extra-granularly. The amendments were added on top of the amount suggested by the SU. This formulation was used and three batches produced consecutively. On comparison to the specifications set by the SU, the three batches were seen to be within the specifications. On comparison to each other, the dissolution profiles were seen to be different. Conclusion and recommendation: The development stage producing batches within the specifications set by the SU but also comparable with regards to its dissolution profile, was seen to be successful. The validation stage was seen to be unsuccessful. Even though the results of the critical parameters were within specifications, when compared to each other, the batches were seen to be significantly different. This led to the research looking at the TT as a whole as being unsuccessful. The researcher then determined what stage could be improved and how this could be done. The various stages seen as having associated problems were determined and ways to mitigate those were determined. A guideline in the form of a flow chart was proposed to aid a manufacturing facility undertaking a TT to shorten the period of time to completion as well as increase the chance of success.
- Full Text:
- Date Issued: 2013
- Authors: Ramloll, Jason
- Date: 2013
- Subjects: Clinical pharmacology Pharmacy -- Research , Pharmaceutical industry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47913 , vital:40398
- Description: Technology transfer (TT) looks at the transfer of intellectual property from one manufacturing site to another. If carried out successfully, a TT can increase the leveraging capability of the company acquiring the intellectual property together with its brand strength. This in turn aids in a decreased time to market of the final dosage form produced. The aim of the research was to assess the TT of an antibacterial oral solid dosage form from one manufacturing site to another. An expected change of manufacturing equipment from a single-pot to a multi-phase system took place due to the equipment available at the receiving unit. The assessment done by the researcher was performed in the capacity of an observer. The assessment of the TT was performed by observing the critical stages during the transfer process, namely the development and validation stages. Prior to the start of the development stage, a characterisation of innovator was performed. At this stage, innovator batches received from the Sending Unit (SU) were characterised to allow for a means of comparison. The development stage allows for the determination of the robustness of the formulation to be used whilst the validation stage will look at the reproducibility of the chosen formulation. During the development stage, small scale trials were manufactured with amendments made to the original formulation. The amendments allowed for a formulation more comparable to the innovator product with regards to its dissolution profile. The comparable batch produced at a small scale was then up-scaled to a production scale batch and these were compared to the innovator products. The amendments made were on the amount of granulation fluid and binder as well as the method of addition of the disintegrant. When a large scale batch comparable to that of the innovator product was produced, the validation stage was started. With the aim of showing reproducibility of the Receiving Unit (RU) at producing large scale batches, three batches were produced. These were tested for all critical parameters, namely through the loss on drying, particle size distribution, hardness, disintegration and dissolution tests and, the results of the tests were compared to the specifications set by the SU. They were also compared to each other, enabling statistical determination of any significant difference across the batches through the use of comparative statistical analyses. Comparison of batches, at the development and validation stage, was done using the dissolution potential of the batches. These were performed through the use of statistical analyses. The RU made use of the similarity factor (F2) to compare the dissolution profiles. For the purpose of this research, the 1-Way analysis of variance was also used, which compared to the similarity factor, took in consideration the level of variance of the batches produced. Results and discussion: During the development stage amendments were made to produce a batch comparable to the innovator product. The amendments that led to the production of a comparable batch consisted of an extra 14 % of granulation fluid as well as 50 % of the disintegrant being added intra-granularly with the other 50 % added extra-granularly. The amendments were added on top of the amount suggested by the SU. This formulation was used and three batches produced consecutively. On comparison to the specifications set by the SU, the three batches were seen to be within the specifications. On comparison to each other, the dissolution profiles were seen to be different. Conclusion and recommendation: The development stage producing batches within the specifications set by the SU but also comparable with regards to its dissolution profile, was seen to be successful. The validation stage was seen to be unsuccessful. Even though the results of the critical parameters were within specifications, when compared to each other, the batches were seen to be significantly different. This led to the research looking at the TT as a whole as being unsuccessful. The researcher then determined what stage could be improved and how this could be done. The various stages seen as having associated problems were determined and ways to mitigate those were determined. A guideline in the form of a flow chart was proposed to aid a manufacturing facility undertaking a TT to shorten the period of time to completion as well as increase the chance of success.
- Full Text:
- Date Issued: 2013
An investigation of short-chain fatty acid profiles and influential gastrointenstinal microbiota associated with irritable bowel syndrome
- Authors: Theunissen, Reza
- Date: 2013
- Subjects: Fatty acids in human nutrition , Gastrointestinal system
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10352 , http://hdl.handle.net/10948/d1020943
- Description: Microbiota are present in large numbers and as a diverse population within the gastrointestinal tract. There are approximately 400 different species of microbiota which may be beneficial, harmful or both, but each play an important role in the regulation and modulation of the hosts’ bowel processes (McOrist et al. 2008; Dethlefsen et al. 2008). Many of these colon microbiota allow for saccharolytic fermentation of non-digestible dietary fibres and carbohydrates into by-products and intermediates, followed by a subsequent conversion into short chain fatty acids (SCFAs) (mainly n-butyric acid, propionic acid and acetic acid) each of which play an important role in maintaining colon homeostasis (Topping & Clifton 2001). A balance of ‘good’ microbiota (e.g., Bacteroides spp./ Bifidobacteria spp.) and ‘bad’ microbiota (e.g., Veilonellae) and the optimal production of various SCFAs within the gut could possibly allow for proper functioning of the large intestine and assist in decreasing the onset of various colonic disorders such as Irritable Bowel Syndrome (IBS). The sample group for the study consists of male and female patients, with an average age of 40 to 50 years old, whom of which have been diagnosed with either constipation IBS (C-IBS) or diarrhoea IBS (D-IBS) via the Rome III criteria system for IBS diagnosis. DNA and SCFA extractions were optimised for human stool, colonic fluid and tissue biopsy sample obtained from the aforementioned patients. Optimization steps allowed for starting material with high analysis integrity. Different methods of microbiota analysis, such as ARISA, were investigated; however, real-time qPCR was selected as the best method to identify and quantify specific microbiota. Extracted SCFAs were separated via gas chromatography and identified and quantified via Mass Spectrometry. Significant changes in microbial content and SCFA profiles were found to be associated with healthy and IBS patients. Results obtained would however be influenced by external factors typical of clinical studies of this nature. This study allows for opportunities for future research into understanding IBS.
- Full Text:
- Date Issued: 2013
- Authors: Theunissen, Reza
- Date: 2013
- Subjects: Fatty acids in human nutrition , Gastrointestinal system
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10352 , http://hdl.handle.net/10948/d1020943
- Description: Microbiota are present in large numbers and as a diverse population within the gastrointestinal tract. There are approximately 400 different species of microbiota which may be beneficial, harmful or both, but each play an important role in the regulation and modulation of the hosts’ bowel processes (McOrist et al. 2008; Dethlefsen et al. 2008). Many of these colon microbiota allow for saccharolytic fermentation of non-digestible dietary fibres and carbohydrates into by-products and intermediates, followed by a subsequent conversion into short chain fatty acids (SCFAs) (mainly n-butyric acid, propionic acid and acetic acid) each of which play an important role in maintaining colon homeostasis (Topping & Clifton 2001). A balance of ‘good’ microbiota (e.g., Bacteroides spp./ Bifidobacteria spp.) and ‘bad’ microbiota (e.g., Veilonellae) and the optimal production of various SCFAs within the gut could possibly allow for proper functioning of the large intestine and assist in decreasing the onset of various colonic disorders such as Irritable Bowel Syndrome (IBS). The sample group for the study consists of male and female patients, with an average age of 40 to 50 years old, whom of which have been diagnosed with either constipation IBS (C-IBS) or diarrhoea IBS (D-IBS) via the Rome III criteria system for IBS diagnosis. DNA and SCFA extractions were optimised for human stool, colonic fluid and tissue biopsy sample obtained from the aforementioned patients. Optimization steps allowed for starting material with high analysis integrity. Different methods of microbiota analysis, such as ARISA, were investigated; however, real-time qPCR was selected as the best method to identify and quantify specific microbiota. Extracted SCFAs were separated via gas chromatography and identified and quantified via Mass Spectrometry. Significant changes in microbial content and SCFA profiles were found to be associated with healthy and IBS patients. Results obtained would however be influenced by external factors typical of clinical studies of this nature. This study allows for opportunities for future research into understanding IBS.
- Full Text:
- Date Issued: 2013
Tolerance intervals for variance component models using a Bayesian simulation procedure
- Authors: Sarpong, Abeam Danso
- Date: 2013
- Subjects: Bayesian statistical decision theory , Multilevel models (Statistics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10583 , http://hdl.handle.net/10948/d1021025
- Description: The estimation of variance components serves as an integral part of the evaluation of variation, and is of interest and required in a variety of applications (Hugo, 2012). Estimation of the among-group variance components is often desired for quantifying the variability and effectively understanding these measurements (Van Der Rijst, 2006). The methodology for determining Bayesian tolerance intervals for the one – way random effects model has originally been proposed by Wolfinger (1998) using both informative and non-informative prior distributions (Hugo, 2012). Wolfinger (1998) also provided relationships with frequentist methodologies. From a Bayesian point of view, it is important to investigate and compare the effect on coverage probabilities if negative variance components are either replaced by zero, or completely disregarded from the simulation process. This research presents a simulation-based approach for determining Bayesian tolerance intervals in variance component models when negative variance components are either replaced by zero, or completely disregarded from the simulation process. This approach handles different kinds of tolerance intervals in a straightforward fashion. It makes use of a computer-generated sample (Monte Carlo process) from the joint posterior distribution of the mean and variance parameters to construct a sample from other relevant posterior distributions. This research makes use of only non-informative Jeffreys‟ prior distributions and uses three Bayesian simulation methods. Comparative results of different tolerance intervals obtained using a method where negative variance components are either replaced by zero or completely disregarded from the simulation process, is investigated and discussed in this research.
- Full Text:
- Date Issued: 2013
- Authors: Sarpong, Abeam Danso
- Date: 2013
- Subjects: Bayesian statistical decision theory , Multilevel models (Statistics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10583 , http://hdl.handle.net/10948/d1021025
- Description: The estimation of variance components serves as an integral part of the evaluation of variation, and is of interest and required in a variety of applications (Hugo, 2012). Estimation of the among-group variance components is often desired for quantifying the variability and effectively understanding these measurements (Van Der Rijst, 2006). The methodology for determining Bayesian tolerance intervals for the one – way random effects model has originally been proposed by Wolfinger (1998) using both informative and non-informative prior distributions (Hugo, 2012). Wolfinger (1998) also provided relationships with frequentist methodologies. From a Bayesian point of view, it is important to investigate and compare the effect on coverage probabilities if negative variance components are either replaced by zero, or completely disregarded from the simulation process. This research presents a simulation-based approach for determining Bayesian tolerance intervals in variance component models when negative variance components are either replaced by zero, or completely disregarded from the simulation process. This approach handles different kinds of tolerance intervals in a straightforward fashion. It makes use of a computer-generated sample (Monte Carlo process) from the joint posterior distribution of the mean and variance parameters to construct a sample from other relevant posterior distributions. This research makes use of only non-informative Jeffreys‟ prior distributions and uses three Bayesian simulation methods. Comparative results of different tolerance intervals obtained using a method where negative variance components are either replaced by zero or completely disregarded from the simulation process, is investigated and discussed in this research.
- Full Text:
- Date Issued: 2013
A model for supporting environmental awereness in higher education using social media
- Authors: Tlebere, Thabo Eugene
- Date: 2013
- Subjects: Social media , Environmental education , Universities and colleges
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:10496 , http://hdl.handle.net/10948/d1020820
- Description: University sustainability is a field of research that has been gaining increased interest in recent years. The reduction of environmental impact has become a strategic objective of universities globally. Universities have been prompted to take necessary action to ensure that their environmental impact is at a minimum. The environmental component of sustainability deals with the current conservation of the earth’s natural resources so that future generations can also have access to them. Human beings, due to their increasing needs, are accountable for the exploitation of natural resources. They are regarded as the main contributors to imbalances in the natural systems. Environmental concerns such as global warming, deforestations, disposal of wastes, and ozone reduction are the outcomes of the damage caused by humans on the environment. The aim of environmental education is to acquire remediation of the environment by making individuals aware of the environment and by educating them about how to live a more sustainable lifestyle. Environmental awareness is perceived as knowledge of the factors that affect the environment and having sensitivity towards the environment. Higher Education Institutions (HEIs) bear the responsibility of educating individuals about environmental issues since they provide education to future leaders in society who may have an influence on future conditions in the environment. Social media are capable of delivering information to a large spectrum of audiences at a low cost. The Pew Internet American Life Project reported that the number of adults who utilise social media has increased by 57 percent from 2005 to 2011. Several environmental activist organisations utilise social media to carry out environmental awareness campaigns. In this study two environmental awareness campaigns which were powered by social media were conducted to improve environmental awareness of individuals in a higher education environment. A Social media Model for ENvironmental Awareness (SMENA) was developed to facilitate the environmental awareness campaigns. The SMENA includes a website, social media as well as theoretical guidelines for creating environmental awareness campaigns, and for using social media for environmental awareness campaigns. A case study at the Nelson Mandela Metropolitan University (NMMU) was used to empirically evaluate SMENA. Students at the Department of Computer Sciences of NMMU were exposed to information about environmental issues through social media with the intention of improving their environmental knowledge and awareness. The SMENA website usability was rated positively and students enjoyed the blogs and information distributed by means of social media. The results of the study intervention were positive and showed that social media can be used to improve the environmental knowledge of students. This study provides a valuable contribution to both the field of environmental education and social media usage and acceptance. The guidelines and requirements for using social media to improve environmental awareness provided in this study can be used to assist educators and university management with addressing the problems of reducing environmental impact.
- Full Text:
- Date Issued: 2013
- Authors: Tlebere, Thabo Eugene
- Date: 2013
- Subjects: Social media , Environmental education , Universities and colleges
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:10496 , http://hdl.handle.net/10948/d1020820
- Description: University sustainability is a field of research that has been gaining increased interest in recent years. The reduction of environmental impact has become a strategic objective of universities globally. Universities have been prompted to take necessary action to ensure that their environmental impact is at a minimum. The environmental component of sustainability deals with the current conservation of the earth’s natural resources so that future generations can also have access to them. Human beings, due to their increasing needs, are accountable for the exploitation of natural resources. They are regarded as the main contributors to imbalances in the natural systems. Environmental concerns such as global warming, deforestations, disposal of wastes, and ozone reduction are the outcomes of the damage caused by humans on the environment. The aim of environmental education is to acquire remediation of the environment by making individuals aware of the environment and by educating them about how to live a more sustainable lifestyle. Environmental awareness is perceived as knowledge of the factors that affect the environment and having sensitivity towards the environment. Higher Education Institutions (HEIs) bear the responsibility of educating individuals about environmental issues since they provide education to future leaders in society who may have an influence on future conditions in the environment. Social media are capable of delivering information to a large spectrum of audiences at a low cost. The Pew Internet American Life Project reported that the number of adults who utilise social media has increased by 57 percent from 2005 to 2011. Several environmental activist organisations utilise social media to carry out environmental awareness campaigns. In this study two environmental awareness campaigns which were powered by social media were conducted to improve environmental awareness of individuals in a higher education environment. A Social media Model for ENvironmental Awareness (SMENA) was developed to facilitate the environmental awareness campaigns. The SMENA includes a website, social media as well as theoretical guidelines for creating environmental awareness campaigns, and for using social media for environmental awareness campaigns. A case study at the Nelson Mandela Metropolitan University (NMMU) was used to empirically evaluate SMENA. Students at the Department of Computer Sciences of NMMU were exposed to information about environmental issues through social media with the intention of improving their environmental knowledge and awareness. The SMENA website usability was rated positively and students enjoyed the blogs and information distributed by means of social media. The results of the study intervention were positive and showed that social media can be used to improve the environmental knowledge of students. This study provides a valuable contribution to both the field of environmental education and social media usage and acceptance. The guidelines and requirements for using social media to improve environmental awareness provided in this study can be used to assist educators and university management with addressing the problems of reducing environmental impact.
- Full Text:
- Date Issued: 2013
Foraging ecology of Cape Gannets (Morus Capensis) at Bird Island, Algoa Bay
- Authors: Green, David Bruce
- Date: 2013
- Subjects: Birds of prey -- Behavior -- South Africa -- Algoa Bay , Gannets -- South Africa -- Algoa Bay , Birds -- Breeding -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10725 , http://hdl.handle.net/10948/d1020790
- Description: The Cape gannet has undergone considerable population change and redistribution over the past 50 years. This has been linked to shifts in the abundance and distribution of their dominant prey, sardine and anchovy. Five breeding colonies, along the west coast of Southern Africa, have shown rapid population declines as a result of reduced prey availability. In contrast, a single colony (Bird Island, Algoa Bay) on the south coast of South Africa has, over the same period, grown fivefold and now supports approximately two thirds of the total population. Due to its conservation importance, and isolation from other breeding localities, it is important to assess the health of the Bird Island colony, and determine how foraging distribution relates to the environment to evaluate current measures of protection. This was achieved through two related studies; a long-term dietary analysis spanning 34 years, and a spatial foraging study, which related three years of tracking data to estimates of prey availability, oceanographic features and marine protected areas (MPAs). The results of the dietary study showed that the dietary constituents of Cape gannets breeding at Bird Island have remained similar over the last three decades, but the importance of sardine and anchovy has increased significantly. For sardine, in particular, this reflects an increased availability of this species (as deduced from hydroacoustic surveys) within the foraging range of the Bird Island colony. The dietary abundance of anchovy was found to be negatively correlated with that of sardine. Surprisingly,.the dietary abundance of anchovy was also negatively correlated with estimates of its availability based on acoustic surveys. The latter is likely to be due to sardine being a preferred prey item. Recent decreases in the dietary contribution of sardine (since 2005) suggest that this species is becoming less available to gannets, with profound implications in terms of nutrient gain associated with foraging. However, this has been mediated by an increase in the dietary contribution of anchovy, which now accounts for the vast majority of prey taken. Spatially, the foraging range of the Bird Island colony expanded during the three years of study, indicating an increase in effort. This increase was likely in an effort to track a distributional change of sardine and anchovy, which showed an apparent westward shift during the study period. There was, however, no evidence of birds tracking features associated with high productivity. This may have been partly due to anomalously warm conditions during the summer of 2012/2013, in which an absence of coastal upwelling prevented surface cooling. Nonetheless, low sea surface temperatures and high chlorophyll a concentrations do not seem to be reliable indicators of important Cape gannet foragingareas. Foraging effort was largely concentrated outside of MPAs, indicating that the current MPA network provides little protection for foraging gannets. This could change with the additional protection of the proposed Greater Addo Elephant National Park MPA expansion, as prey species are allowed to recover following the removal of fishing pressure. Overall, the colony appears to be in good condition as the diet is still dominated by live prey items, and the foraging range remains smaller than many of the colonies along the west coast. However, it is important that monitoring be continued, in particular with respect to changes in the availability of sardine and anchovy. Long-term shifts of these species out of the colony‘s foraging range could negatively influence the population in the future. This might be worsened by interspecific competition for prey resources. Considering the conservation importance of this population, maintenance of healthy prey stocks within the home range of breeding Cape gannets should be prioritised in order to prevent declines similar to those observed at west coast colonies.
- Full Text:
- Date Issued: 2013
- Authors: Green, David Bruce
- Date: 2013
- Subjects: Birds of prey -- Behavior -- South Africa -- Algoa Bay , Gannets -- South Africa -- Algoa Bay , Birds -- Breeding -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10725 , http://hdl.handle.net/10948/d1020790
- Description: The Cape gannet has undergone considerable population change and redistribution over the past 50 years. This has been linked to shifts in the abundance and distribution of their dominant prey, sardine and anchovy. Five breeding colonies, along the west coast of Southern Africa, have shown rapid population declines as a result of reduced prey availability. In contrast, a single colony (Bird Island, Algoa Bay) on the south coast of South Africa has, over the same period, grown fivefold and now supports approximately two thirds of the total population. Due to its conservation importance, and isolation from other breeding localities, it is important to assess the health of the Bird Island colony, and determine how foraging distribution relates to the environment to evaluate current measures of protection. This was achieved through two related studies; a long-term dietary analysis spanning 34 years, and a spatial foraging study, which related three years of tracking data to estimates of prey availability, oceanographic features and marine protected areas (MPAs). The results of the dietary study showed that the dietary constituents of Cape gannets breeding at Bird Island have remained similar over the last three decades, but the importance of sardine and anchovy has increased significantly. For sardine, in particular, this reflects an increased availability of this species (as deduced from hydroacoustic surveys) within the foraging range of the Bird Island colony. The dietary abundance of anchovy was found to be negatively correlated with that of sardine. Surprisingly,.the dietary abundance of anchovy was also negatively correlated with estimates of its availability based on acoustic surveys. The latter is likely to be due to sardine being a preferred prey item. Recent decreases in the dietary contribution of sardine (since 2005) suggest that this species is becoming less available to gannets, with profound implications in terms of nutrient gain associated with foraging. However, this has been mediated by an increase in the dietary contribution of anchovy, which now accounts for the vast majority of prey taken. Spatially, the foraging range of the Bird Island colony expanded during the three years of study, indicating an increase in effort. This increase was likely in an effort to track a distributional change of sardine and anchovy, which showed an apparent westward shift during the study period. There was, however, no evidence of birds tracking features associated with high productivity. This may have been partly due to anomalously warm conditions during the summer of 2012/2013, in which an absence of coastal upwelling prevented surface cooling. Nonetheless, low sea surface temperatures and high chlorophyll a concentrations do not seem to be reliable indicators of important Cape gannet foragingareas. Foraging effort was largely concentrated outside of MPAs, indicating that the current MPA network provides little protection for foraging gannets. This could change with the additional protection of the proposed Greater Addo Elephant National Park MPA expansion, as prey species are allowed to recover following the removal of fishing pressure. Overall, the colony appears to be in good condition as the diet is still dominated by live prey items, and the foraging range remains smaller than many of the colonies along the west coast. However, it is important that monitoring be continued, in particular with respect to changes in the availability of sardine and anchovy. Long-term shifts of these species out of the colony‘s foraging range could negatively influence the population in the future. This might be worsened by interspecific competition for prey resources. Considering the conservation importance of this population, maintenance of healthy prey stocks within the home range of breeding Cape gannets should be prioritised in order to prevent declines similar to those observed at west coast colonies.
- Full Text:
- Date Issued: 2013
Production of recombinant human CD21 and CD23 : towards a better understanding of their interaction
- Authors: Van Zyl, Dwain George
- Date: 2013
- Subjects: Immunoglobulins , Fc receptors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10365 , http://hdl.handle.net/10948/d10211135
- Description: The prevalence of allergic diseases has dramatically increased over the last three decades. Presently, it is estimated that 20-30 per cent of the developed world suffers from allergic diseases. The majority of allergic diseases are rooted in the activities of IgE; an immunoglobulin which exerts its effector functions by interacting with a network of proteins. This network includes its low affinity receptor CD23. Cross linking of membrane IgE and CD21 by soluble CD23 results in an increase in IgE synthesis. This marks the interaction between CD23 and CD21 as an attractive therapeutic target. However, details regarding this interaction are inadequate for rational drug design. To obtain a deeper understanding of the CD23-CD21 interaction recombinant human CD21 (SCR1-2 and SCR5-8) and CD23 (16 kD and 25 kDa) were produced. The cloning, expression and purification of recombinant proteins comprised a significant portion of this study. Recombinant CD23 was expressed as inclusion bodies, refolded by rapid dilution and purified by size exclusion chromatography. Conversely, recombinant CD21 was expressed as soluble MBP-fusions and purified with an amylose affinity resin. The interaction between recombinant CD23 and CD21 was analysed by flow cytometry and ELISA experiments. Flow cytometry showed that 16 kDa and 25 kDa CD23 interacted with SCR5-8 to the same extent. Semi-quantitative ELISA experiments showed that both SCR1-2 and SCR5-8 were able to interact with 16 kDa and 25 kDa CD23. This suggests that the binding sites of SCR1-2 and SCR5-8 occur on 16 kDa CD23. Furthermore, since proteins were expressed in E. coli it suggests that the CD23-CD21 interaction does not require glycosylation. Furthermore, considering what is known about the SCR1-2-CD23 interaction from previous NMR studies; i.e. that the C-terminal tail (residues residues 289-298) of CD23 is responsible for binding SCR1-2, indicates that SCR5-8 binds somewhere within the lectin domain of CD23. This indicates that the CD23-CD21 interaction involves C-terminal tail-SCR1-2 and lectin domain-SCR5-8 interactions.
- Full Text:
- Date Issued: 2013
- Authors: Van Zyl, Dwain George
- Date: 2013
- Subjects: Immunoglobulins , Fc receptors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10365 , http://hdl.handle.net/10948/d10211135
- Description: The prevalence of allergic diseases has dramatically increased over the last three decades. Presently, it is estimated that 20-30 per cent of the developed world suffers from allergic diseases. The majority of allergic diseases are rooted in the activities of IgE; an immunoglobulin which exerts its effector functions by interacting with a network of proteins. This network includes its low affinity receptor CD23. Cross linking of membrane IgE and CD21 by soluble CD23 results in an increase in IgE synthesis. This marks the interaction between CD23 and CD21 as an attractive therapeutic target. However, details regarding this interaction are inadequate for rational drug design. To obtain a deeper understanding of the CD23-CD21 interaction recombinant human CD21 (SCR1-2 and SCR5-8) and CD23 (16 kD and 25 kDa) were produced. The cloning, expression and purification of recombinant proteins comprised a significant portion of this study. Recombinant CD23 was expressed as inclusion bodies, refolded by rapid dilution and purified by size exclusion chromatography. Conversely, recombinant CD21 was expressed as soluble MBP-fusions and purified with an amylose affinity resin. The interaction between recombinant CD23 and CD21 was analysed by flow cytometry and ELISA experiments. Flow cytometry showed that 16 kDa and 25 kDa CD23 interacted with SCR5-8 to the same extent. Semi-quantitative ELISA experiments showed that both SCR1-2 and SCR5-8 were able to interact with 16 kDa and 25 kDa CD23. This suggests that the binding sites of SCR1-2 and SCR5-8 occur on 16 kDa CD23. Furthermore, since proteins were expressed in E. coli it suggests that the CD23-CD21 interaction does not require glycosylation. Furthermore, considering what is known about the SCR1-2-CD23 interaction from previous NMR studies; i.e. that the C-terminal tail (residues residues 289-298) of CD23 is responsible for binding SCR1-2, indicates that SCR5-8 binds somewhere within the lectin domain of CD23. This indicates that the CD23-CD21 interaction involves C-terminal tail-SCR1-2 and lectin domain-SCR5-8 interactions.
- Full Text:
- Date Issued: 2013
Evaluation of eucalyptus citriodora derived p-menthane-3,8-diol-citronellal acetal as a bio-plasticizer for cosmetic application
- Authors: Burger, Kirstin
- Date: 2013
- Subjects: Plasticizers , Eucalyptus citriodora
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10420 , http://hdl.handle.net/10948/d1014080
- Description: Plasticizers are generally added to cosmetic and personal care products to improve the filmforming abilities of the product and increase flexibility of the film formed on the skin or hair surface. For example, plasticizers are present in perfumes to prolong the release of the specific scent, which is the ultimate goal in a good quality perfume. Plasticizers in nail varnishes prevent chipping, improve the aesthetics by adhering to the keratin in the nail which means the coating stays on for much longer, which is the ultimate goal in nail products. Plasticizers improve the gloss, resist chipping and allow quick drying time. Therefore it can be seen that plasticizers play a vital role in personal care products like perfumes and nail varnishes. Certain plasticizers e.g. phthalates, can cause problems associated with human health and can harm the environment. They are easily available and large volumes can be obtained at a low cost. These phthalates, for example, di-butyl phthalate (DBP) have been identified as carcinogenic. Nowadays the occurrence of cancer is rapidly increasing. The plasticizers present in a large number of consumer and personal care products, can possibly be linked to the ever increasing reports of cancer. Therefore a substitute to the traditional phthalate plasticizers must be investigated. The aim of this research is to produce a plasticizer derived from naturally occurring Eucalyptus oil, which can be used to replace the existing plasticizers in cosmetic formulations. Para-menthane-3,8-diol (PMD), occurring naturally in the oil from the tree, Eucalyptus citriodora, forms an acetal with citronellal (PMD, acetal, citronellal all occur naturally in the oil). It has been previously shown that PMD-citronellal acetal will exhibit plasticizing properties similar to conventional plasticizers. The objective was to enhance the formation of the acetal in the Eucalyptus oil by reacting it with excess PMD. An effective synthesis method for the PMD-citronellal acetal enriched oil (~73.8 percent) was determined from optimization experiments. The physical characterisation of the PMD-citronellal acetal enriched oil was done and compared with that of DBP. The acetal-enriched oil had a lower density, slightly higher solubility in water (at 25°C), lower refractive index (Brix percent) and a higher boiling point (350°C) than DBP. The physical characteristics of the Eucalyptus oil source and the acetal-enriched Eucalyptus oil were very similar. This can be expected as the Eucalyptus oil consists of ~84.3 percent Citronellal, ~ 1.3 percent PMD and 2.7 percent PMD-citronellal acetal. In this study the effectiveness of the acetal-enriched Eucalyptus oil (referred to from now on as the bio-plasticizer) was compared to a conventional plasticizer such as di-butyl phthalate (DBP), commonly used in cosmetic products. Two cosmetic formulations were produced: a nail varnish and a perfume formulation. Various tests were performed on these formulations to investigate the plasticizing properties of the bio-plasticizer. The objectives were to determine if the natural plasticizer is as effective as the potentially carcinogenic phthalate plasticizers and can be used as a substitute for the phthalates in personal care products. The results indicate that the bio-plasticizer does behave similarly to di-butyl phthalate, however, the effectiveness of the bio-plasticizer is lower than that of di-butyl phthalate. As the viscosity of the synthesized oil was high, this affected the overall consistency of the products. A more viscous nail varnish and perfume was produced in comparison to the DBP counterpart. The stability of the bio-plasticizer in the cosmetic formulations of nail varnish and perfume was also investigated. The cosmetic products were incubated at 0°C, 25°C and 40°C over a period of two months. Any changes in colour, odour, pH, refractive index, separation and plasticizer peak change in the gas chromatogram trace were recorded. It was determined that the PMD-citronellal acetal-enriched oil was relatively unstable under elevated temperatures and light intensity. Storage under higher temperatures (40°C) tends to increase the acidity. Therefore the bio-plasticizer must be placed in a closed, covered bottle and stored in an environment away from light and elevated temperatures. According to the gas chromatogram peaks, it was clear that both the bio-plasticizer and the DBP were more unstable in the perfume formulation than in the nail polish and were especially sensitive to light when in the perfume. This could possibly be due to the interaction with the fragrance molecule, p-anisaldehyde.
- Full Text:
- Date Issued: 2013
- Authors: Burger, Kirstin
- Date: 2013
- Subjects: Plasticizers , Eucalyptus citriodora
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10420 , http://hdl.handle.net/10948/d1014080
- Description: Plasticizers are generally added to cosmetic and personal care products to improve the filmforming abilities of the product and increase flexibility of the film formed on the skin or hair surface. For example, plasticizers are present in perfumes to prolong the release of the specific scent, which is the ultimate goal in a good quality perfume. Plasticizers in nail varnishes prevent chipping, improve the aesthetics by adhering to the keratin in the nail which means the coating stays on for much longer, which is the ultimate goal in nail products. Plasticizers improve the gloss, resist chipping and allow quick drying time. Therefore it can be seen that plasticizers play a vital role in personal care products like perfumes and nail varnishes. Certain plasticizers e.g. phthalates, can cause problems associated with human health and can harm the environment. They are easily available and large volumes can be obtained at a low cost. These phthalates, for example, di-butyl phthalate (DBP) have been identified as carcinogenic. Nowadays the occurrence of cancer is rapidly increasing. The plasticizers present in a large number of consumer and personal care products, can possibly be linked to the ever increasing reports of cancer. Therefore a substitute to the traditional phthalate plasticizers must be investigated. The aim of this research is to produce a plasticizer derived from naturally occurring Eucalyptus oil, which can be used to replace the existing plasticizers in cosmetic formulations. Para-menthane-3,8-diol (PMD), occurring naturally in the oil from the tree, Eucalyptus citriodora, forms an acetal with citronellal (PMD, acetal, citronellal all occur naturally in the oil). It has been previously shown that PMD-citronellal acetal will exhibit plasticizing properties similar to conventional plasticizers. The objective was to enhance the formation of the acetal in the Eucalyptus oil by reacting it with excess PMD. An effective synthesis method for the PMD-citronellal acetal enriched oil (~73.8 percent) was determined from optimization experiments. The physical characterisation of the PMD-citronellal acetal enriched oil was done and compared with that of DBP. The acetal-enriched oil had a lower density, slightly higher solubility in water (at 25°C), lower refractive index (Brix percent) and a higher boiling point (350°C) than DBP. The physical characteristics of the Eucalyptus oil source and the acetal-enriched Eucalyptus oil were very similar. This can be expected as the Eucalyptus oil consists of ~84.3 percent Citronellal, ~ 1.3 percent PMD and 2.7 percent PMD-citronellal acetal. In this study the effectiveness of the acetal-enriched Eucalyptus oil (referred to from now on as the bio-plasticizer) was compared to a conventional plasticizer such as di-butyl phthalate (DBP), commonly used in cosmetic products. Two cosmetic formulations were produced: a nail varnish and a perfume formulation. Various tests were performed on these formulations to investigate the plasticizing properties of the bio-plasticizer. The objectives were to determine if the natural plasticizer is as effective as the potentially carcinogenic phthalate plasticizers and can be used as a substitute for the phthalates in personal care products. The results indicate that the bio-plasticizer does behave similarly to di-butyl phthalate, however, the effectiveness of the bio-plasticizer is lower than that of di-butyl phthalate. As the viscosity of the synthesized oil was high, this affected the overall consistency of the products. A more viscous nail varnish and perfume was produced in comparison to the DBP counterpart. The stability of the bio-plasticizer in the cosmetic formulations of nail varnish and perfume was also investigated. The cosmetic products were incubated at 0°C, 25°C and 40°C over a period of two months. Any changes in colour, odour, pH, refractive index, separation and plasticizer peak change in the gas chromatogram trace were recorded. It was determined that the PMD-citronellal acetal-enriched oil was relatively unstable under elevated temperatures and light intensity. Storage under higher temperatures (40°C) tends to increase the acidity. Therefore the bio-plasticizer must be placed in a closed, covered bottle and stored in an environment away from light and elevated temperatures. According to the gas chromatogram peaks, it was clear that both the bio-plasticizer and the DBP were more unstable in the perfume formulation than in the nail polish and were especially sensitive to light when in the perfume. This could possibly be due to the interaction with the fragrance molecule, p-anisaldehyde.
- Full Text:
- Date Issued: 2013
Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands
- Authors: Habarurema, Gratien
- Date: 2013
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10441 , http://hdl.handle.net/10948/d1020952
- Description: This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the synthesis of tridentate, tetradentate and pentadentate Schiff bases ligands derived from the condensation reactions of benzaldehyde with different primary amines. The structures of these Schiff bases and their complexes were confirmed by using physical characterization methods, namely melting points, UV-Visible, UV-emission, 1H NMR and IR spectroscopy, X-ray diffractometry and elemental analysis. To further understand the coordination chemistry of rhenium, the prepared diiminediphenol N2O2-donor Schiff base ligand N N′-o-phenylene-bis(salicylaldimine) (H2salphen) was reacted with trans-[ReOCl3(PPh3)2] to yield cis-[ReCl2(ophsal)(PPh3)], whereas its reaction with trans-[ReOBr3(PPh3)2] resulted in the formation of the cis-[ReBr2(aphsal)(PPh3)].2CH3CN complex. In the above complexes the H2salphen ligand was cleaved leading to the coordinated tridentate ophsal NO2- and aphsal N2O-donor ligands. The reaction of H3aphsal with trans-[ReOBr3(PPh3)2] in toluene led to an unexpected compound, trans- [{[ReBr(aphsal)(PPh3)2]Br}{[ReBr(aphsal)(PPh3)2](ReO4)}] with an imido [ReNR]3+core. The ligand aphsal was coordinated tridentately with the doubly deprotonated amino nitrogen leading to Re(V)-imido complexes. The reaction of 2-((Z)-(2-aminoethylimino)methyl)phenol (H3amphol) with [Re(CO)5Cl] led to the rhenium(I) product fac-[Re(CO)3(H3amphol)] with H3amphol coordinated as a monoanionic tridentate chelate through its phenolate oxygen and amino nitrogen atoms. The X-ray crystal structures showed that all complexes display a distorted octahedral geometry around the central rhenium atom. The reaction of 2,6-bis(2-hydroxyphenylimino)pyridine (H2hpp) with cis-[ReO2I(PPh3)2] resulted in the reduced Re(III) product trans-[Re(hpp)(PPh3)2]I, while trans-[Re(hpp)(PPh3)2](ReO4) was isolated from its reaction with trans-[ReOCl3(PPh3)2]. The H2hpp ligand acts as a pentadentate N3O2-donor ligand where the two phenolic protons undergo deprotonation and its three nitrogens act as neutral donor atoms. Both compounds resulted from a disproportionation reaction characterized by the produced perrhenate counter-ion. The complex fac-[Re(CO)3(H2hpp)Cl] was prepared from [Re(CO)5Cl] and H2hpp in toluene. The H2hpp ligand acted as a neutral bidentate N,N-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, two neutral nitrogen atoms and a chloride ligand. The reactions of the potentially tetradentate ligand N,N'-ethylenebis(salicylideneimine) (H2salen) with different rhenium(V) precursors resulted in the formation of two dimeric oxorhenium (V) compounds. In the reaction of H2salen with trans-[ReOCl3(PPh3)2] in ethanol, the highly unusual distorted dimeric complex (μ-salen)[ReOCl2(PPh3)]2 was isolated, in which salen2- is coordinated as a tetradentate to two oxorhenium(V) centres, and salen2- is present as a bidentate monoanionic ligand on each rhenium center. The reaction of cis- [ReO2I(PPh3)2] with H2salen led to the formation of the neutral dimeric oxorhenium(V) complex (μ-O)[ReO(salen)]2 in which the tetradentate chelate salen acts as a tetradentate dianionic ligand through its phenolate oxygens and nitrogen atoms of the azomethine groups. In its reaction with H2hmp the compound (μ-O)[ReO(hmp)]2 was isolated. In this product the pentadentate ligand H2hmp coordinated as tetradentate via its phenolic oxygen and nitrogen atoms. The reaction of the potentially tetradentate N1,N2-bis(aminobenzylidene)-1,2-ethylenediamine (H2amben) with trans-[ReOCl3(PPh3)2] led to the formation of the monocationic square-pyramidal complex salt [ReO(amben)](ReO4.
- Full Text:
- Date Issued: 2013
- Authors: Habarurema, Gratien
- Date: 2013
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10441 , http://hdl.handle.net/10948/d1020952
- Description: This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the synthesis of tridentate, tetradentate and pentadentate Schiff bases ligands derived from the condensation reactions of benzaldehyde with different primary amines. The structures of these Schiff bases and their complexes were confirmed by using physical characterization methods, namely melting points, UV-Visible, UV-emission, 1H NMR and IR spectroscopy, X-ray diffractometry and elemental analysis. To further understand the coordination chemistry of rhenium, the prepared diiminediphenol N2O2-donor Schiff base ligand N N′-o-phenylene-bis(salicylaldimine) (H2salphen) was reacted with trans-[ReOCl3(PPh3)2] to yield cis-[ReCl2(ophsal)(PPh3)], whereas its reaction with trans-[ReOBr3(PPh3)2] resulted in the formation of the cis-[ReBr2(aphsal)(PPh3)].2CH3CN complex. In the above complexes the H2salphen ligand was cleaved leading to the coordinated tridentate ophsal NO2- and aphsal N2O-donor ligands. The reaction of H3aphsal with trans-[ReOBr3(PPh3)2] in toluene led to an unexpected compound, trans- [{[ReBr(aphsal)(PPh3)2]Br}{[ReBr(aphsal)(PPh3)2](ReO4)}] with an imido [ReNR]3+core. The ligand aphsal was coordinated tridentately with the doubly deprotonated amino nitrogen leading to Re(V)-imido complexes. The reaction of 2-((Z)-(2-aminoethylimino)methyl)phenol (H3amphol) with [Re(CO)5Cl] led to the rhenium(I) product fac-[Re(CO)3(H3amphol)] with H3amphol coordinated as a monoanionic tridentate chelate through its phenolate oxygen and amino nitrogen atoms. The X-ray crystal structures showed that all complexes display a distorted octahedral geometry around the central rhenium atom. The reaction of 2,6-bis(2-hydroxyphenylimino)pyridine (H2hpp) with cis-[ReO2I(PPh3)2] resulted in the reduced Re(III) product trans-[Re(hpp)(PPh3)2]I, while trans-[Re(hpp)(PPh3)2](ReO4) was isolated from its reaction with trans-[ReOCl3(PPh3)2]. The H2hpp ligand acts as a pentadentate N3O2-donor ligand where the two phenolic protons undergo deprotonation and its three nitrogens act as neutral donor atoms. Both compounds resulted from a disproportionation reaction characterized by the produced perrhenate counter-ion. The complex fac-[Re(CO)3(H2hpp)Cl] was prepared from [Re(CO)5Cl] and H2hpp in toluene. The H2hpp ligand acted as a neutral bidentate N,N-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, two neutral nitrogen atoms and a chloride ligand. The reactions of the potentially tetradentate ligand N,N'-ethylenebis(salicylideneimine) (H2salen) with different rhenium(V) precursors resulted in the formation of two dimeric oxorhenium (V) compounds. In the reaction of H2salen with trans-[ReOCl3(PPh3)2] in ethanol, the highly unusual distorted dimeric complex (μ-salen)[ReOCl2(PPh3)]2 was isolated, in which salen2- is coordinated as a tetradentate to two oxorhenium(V) centres, and salen2- is present as a bidentate monoanionic ligand on each rhenium center. The reaction of cis- [ReO2I(PPh3)2] with H2salen led to the formation of the neutral dimeric oxorhenium(V) complex (μ-O)[ReO(salen)]2 in which the tetradentate chelate salen acts as a tetradentate dianionic ligand through its phenolate oxygens and nitrogen atoms of the azomethine groups. In its reaction with H2hmp the compound (μ-O)[ReO(hmp)]2 was isolated. In this product the pentadentate ligand H2hmp coordinated as tetradentate via its phenolic oxygen and nitrogen atoms. The reaction of the potentially tetradentate N1,N2-bis(aminobenzylidene)-1,2-ethylenediamine (H2amben) with trans-[ReOCl3(PPh3)2] led to the formation of the monocationic square-pyramidal complex salt [ReO(amben)](ReO4.
- Full Text:
- Date Issued: 2013
Hydrothermal liquefaction of scenedesmus obliquus in a continuous reactor system
- Authors: Kaufmann, Gideon
- Date: 2013
- Subjects: Biomass chemicals Microalgae -- Biotechnology , Supercritical fluids
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/47878 , vital:40393
- Description: In 2009 InnoVenton, a research institute at the Nelson Mandela Metropolitan University (NMMU) set out to establish a technological concept of micro-algae to fuel, at which point an algae farm was established. The overall research strategy is envisaged to focus on a number of potential uses of algae biomass and related processes such as water treatment can take place, the binding of the biomass to coal fines to create briquettes are possible, and bio crude production from direct liquefaction. This project will focus on the latter. In 2010 a partnership between NMMU and the University of Cape Town’s (UCT) Department of Chemical Engineering was established to design, construct and commission a test unit that could convert the algae biomass into a pumpable bio crude by the liquefaction process. During the initial operation of this test unit, flow problems of the reaction product were observed. As such, the aim of this study is to investigate a number of process conditions and develop strategies to minimise or alleviate this problem. As part of this study, UCT will replicate the NMMU test unit in Cape Town in order to start focussing on finding relevant solutions to the problems which exist. Presently continuous reactor systems are not used for the liquefaction of micro-algae. According to Toor, et al(2011)¹ Other feedstocks have been placed in continuous reactor systems with good end results. They continue to write in their review that batch systems were used in most experiments. If micro-algae are to become a competitive alternative to crude oil then batch systems are not the way forward. From a commercial and efficiency standpoint, there are significant advantages to move from typical batch reactors to continuous reactors, specifically in terms of downtime and loading/unloading of vessels. From the evidence gathered in Port Elizabeth, the nature of the reaction product caused typical plugflow reactor systems to block. The aim of this study is to investigate possible solutions to the problem of the reactor system blockage and thus pave the way for the implementation of a continuous reactor system. There are many variables which can be manipulated to achieve success for example the use of catalysts, co-feeding of reactant gases like hydrogen, residence time, temperature or pressure. Manipulating these variable can help to change conversion and/or product spectrum. The results of this study will be compared to results obtained by typical batch experimentation conducted at NMMU. This research varied temperature only. This variation was effective enough to find solutions to the obstacles that were present. Once the algae feedstock was being diverted to the vent pot via the safety relief valve, it was understood that something was blocked. Once the reactor was cooled and removed, it was apparent that the reactor was not blocking up however the exit line to the product catch pot was. To solve this problem a new heated zone was created. This heated the exit line and the top of the product catch pot to around 50°C below the reaction temperature. This upgrade to the system made the oil liquor less vicous and flow easier. The exit line never blocked up again during the research. Energy values of the product were comparable to that of coal. Higher reaction temperatures favoured the production of paraffins and olefins while lower reaction temperatures favoured the production of oxygenates. An ampoule sampler was introduced to take samples of the gas exit line. The comprehensive gas chromatography analysis of the gas in the ampoules revealed that eventhough the concentration of the products present were low, there were significant quantities of paraffins present in the gas stream. More research and the variation of variables discussed previously need to be conducted. It is also apparent that the test unit needs to be upgraded to a bigger reactor and possibly to use materials of construction which do not corrode easily. A computer model could be developed in conjunction with the current test unit and then a bigger reactor might not be needed. The reducing of the oxygen content in the final bio crude also needs to be investigated. Overall the research is very promising in the fact that the final bio crude that was produced is comparable to coal. With further research it will be possible to create a product that is comparable to fossil crude oil and then could be used as a supplement to crude oil.
- Full Text:
- Date Issued: 2013
- Authors: Kaufmann, Gideon
- Date: 2013
- Subjects: Biomass chemicals Microalgae -- Biotechnology , Supercritical fluids
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/47878 , vital:40393
- Description: In 2009 InnoVenton, a research institute at the Nelson Mandela Metropolitan University (NMMU) set out to establish a technological concept of micro-algae to fuel, at which point an algae farm was established. The overall research strategy is envisaged to focus on a number of potential uses of algae biomass and related processes such as water treatment can take place, the binding of the biomass to coal fines to create briquettes are possible, and bio crude production from direct liquefaction. This project will focus on the latter. In 2010 a partnership between NMMU and the University of Cape Town’s (UCT) Department of Chemical Engineering was established to design, construct and commission a test unit that could convert the algae biomass into a pumpable bio crude by the liquefaction process. During the initial operation of this test unit, flow problems of the reaction product were observed. As such, the aim of this study is to investigate a number of process conditions and develop strategies to minimise or alleviate this problem. As part of this study, UCT will replicate the NMMU test unit in Cape Town in order to start focussing on finding relevant solutions to the problems which exist. Presently continuous reactor systems are not used for the liquefaction of micro-algae. According to Toor, et al(2011)¹ Other feedstocks have been placed in continuous reactor systems with good end results. They continue to write in their review that batch systems were used in most experiments. If micro-algae are to become a competitive alternative to crude oil then batch systems are not the way forward. From a commercial and efficiency standpoint, there are significant advantages to move from typical batch reactors to continuous reactors, specifically in terms of downtime and loading/unloading of vessels. From the evidence gathered in Port Elizabeth, the nature of the reaction product caused typical plugflow reactor systems to block. The aim of this study is to investigate possible solutions to the problem of the reactor system blockage and thus pave the way for the implementation of a continuous reactor system. There are many variables which can be manipulated to achieve success for example the use of catalysts, co-feeding of reactant gases like hydrogen, residence time, temperature or pressure. Manipulating these variable can help to change conversion and/or product spectrum. The results of this study will be compared to results obtained by typical batch experimentation conducted at NMMU. This research varied temperature only. This variation was effective enough to find solutions to the obstacles that were present. Once the algae feedstock was being diverted to the vent pot via the safety relief valve, it was understood that something was blocked. Once the reactor was cooled and removed, it was apparent that the reactor was not blocking up however the exit line to the product catch pot was. To solve this problem a new heated zone was created. This heated the exit line and the top of the product catch pot to around 50°C below the reaction temperature. This upgrade to the system made the oil liquor less vicous and flow easier. The exit line never blocked up again during the research. Energy values of the product were comparable to that of coal. Higher reaction temperatures favoured the production of paraffins and olefins while lower reaction temperatures favoured the production of oxygenates. An ampoule sampler was introduced to take samples of the gas exit line. The comprehensive gas chromatography analysis of the gas in the ampoules revealed that eventhough the concentration of the products present were low, there were significant quantities of paraffins present in the gas stream. More research and the variation of variables discussed previously need to be conducted. It is also apparent that the test unit needs to be upgraded to a bigger reactor and possibly to use materials of construction which do not corrode easily. A computer model could be developed in conjunction with the current test unit and then a bigger reactor might not be needed. The reducing of the oxygen content in the final bio crude also needs to be investigated. Overall the research is very promising in the fact that the final bio crude that was produced is comparable to coal. With further research it will be possible to create a product that is comparable to fossil crude oil and then could be used as a supplement to crude oil.
- Full Text:
- Date Issued: 2013
Synthesis of fluorescent polymers with coumarin backbones by "click" polymerization
- Authors: Okerio, Jaspher Mosomi
- Date: 2013
- Subjects: Polymerization , Fluorescent polymers
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10431 , http://hdl.handle.net/10948/d1020132
- Description: Click chemistry is one of the growing areas of research which is applied in the design and synthesis of a wide range of polymeric architectures. This investigation focuses on the synthesis of fluorescent coumarin based polymers by “click” A-B step growth polymerization process and evaluation of their photophysical properties. Non-fluorescent azide-alkyne functionalized coumarin-based monomers were synthesized in multiple steps from 2,4-dihydroxybenzaldehyde in reasonable yields. Polymers with coumarin backbone were synthesized from azide-alkyne functionalized coumarin monomers via the Cu(I) catalyzed 1,3-dipolar cycloaddition reaction between azides and alkynes, a typical click reaction, to form polymers whose repeating units are connected by a 1,2,3-triazole ring. The structures of the synthesized polymers were confirmed by NMR and FT-IR spectroscopy. Finally, the photophysical properties of the synthesized monomers and polymers were evaluated in DMF. All coumarin based monomers showed reduced fluorescent properties due to the quenching effect from the azido group. Although all polymers absorbed at maximum wavelength of 340 nm, a characteristic for coumarin chromophore, the homo-polymers emitted at a shorter wavelength of 413 nm as compared to the co-polymers which emitted at 421 nm.
- Full Text:
- Date Issued: 2013
- Authors: Okerio, Jaspher Mosomi
- Date: 2013
- Subjects: Polymerization , Fluorescent polymers
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10431 , http://hdl.handle.net/10948/d1020132
- Description: Click chemistry is one of the growing areas of research which is applied in the design and synthesis of a wide range of polymeric architectures. This investigation focuses on the synthesis of fluorescent coumarin based polymers by “click” A-B step growth polymerization process and evaluation of their photophysical properties. Non-fluorescent azide-alkyne functionalized coumarin-based monomers were synthesized in multiple steps from 2,4-dihydroxybenzaldehyde in reasonable yields. Polymers with coumarin backbone were synthesized from azide-alkyne functionalized coumarin monomers via the Cu(I) catalyzed 1,3-dipolar cycloaddition reaction between azides and alkynes, a typical click reaction, to form polymers whose repeating units are connected by a 1,2,3-triazole ring. The structures of the synthesized polymers were confirmed by NMR and FT-IR spectroscopy. Finally, the photophysical properties of the synthesized monomers and polymers were evaluated in DMF. All coumarin based monomers showed reduced fluorescent properties due to the quenching effect from the azido group. Although all polymers absorbed at maximum wavelength of 340 nm, a characteristic for coumarin chromophore, the homo-polymers emitted at a shorter wavelength of 413 nm as compared to the co-polymers which emitted at 421 nm.
- Full Text:
- Date Issued: 2013
The production of Omega 3 fatty acids by a mixed microalgae culture
- Authors: Kimono, Diana Agnes
- Date: 2013
- Subjects: Omega-3 fatty acids , Algae culture , Microalgae
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/6498 , vital:21097
- Description: Background and Aim: Microalgae are a potential economical source of omega-3 fatty acids, which are known for their health benefits. Omega-3 fatty acids derived from microalgae are however still expensive due to high costs involved in production. These costs can partly be attributed to cultivation of microalgae in unialgal cultures, which are prone to contamination, difficult to scale up and require stringent control of growth conditions. This study therefore is aimed to investigate the feasibility of using a mixed microalgae culture for the production of omega-3 fatty acids. Methods and materials: The microalgae were grown under uncontrolled conditions in a hanging-bag photo-bioreactor, with only the phosphorus-nitrogen ratio (P:N-ratio) varied. Variations in the different population proportions in the culture were studied and related to the biomass, total fatty acid and omega-3 fatty acid productivity of the culture. Finally, a comparison was made between the results obtained in this study and similar studies found in literature. Results and discussion: The mixed culture used was composed of several green microalgae, whose proportions varied with P:N-ratio, season, and age of the culture. Different interactions between the populations were observable, and these were thought to influence the culture’s biomass, total fatty acids (TFAs) and omega-3 fatty acid productivity. The TFA content of the culture was ~10-20% by the end of the exponential phase, depending on the nutrients supplied. The fatty acids were composed of mostly unsaturated fatty acids, the majority of which were omega-3 fatty acids; C18:3ω3 (up to 50% of TFA), C16:4ω3 (up to 15%) and C18:4ω3 (up to 5%). Other fatty acids observed included C16:0 (up to 25%), C18:1ω9/C18:1ω8 (up to 20%), C18:2ω6 (up to 5%), traces of C18:0, C18:3ω6, C17:0, C16:3ω3 and C16:1ω7 were also detected. The presence of these fatty acids was found to vary depending on season, P:N-ratio, and age of the culture. When compared to studies in the literature, the mixed culture was found to perform better than, or as well as reported studies, where unialgal cultures were cultivated under controlled laboratory conditions. Conclusion: In view of the reported advantages of cultivating mixed cultures, the production of omega-3 fatty acids via such cultures appears attractive. More research however is needed to optimise the culture; study interactions between the organisms and their effect on biomass, total fatty acid and omega-3 fatty acid productivity. Finally, the economic implications of using mixed cultures need to be evaluated as well.
- Full Text:
- Date Issued: 2013
- Authors: Kimono, Diana Agnes
- Date: 2013
- Subjects: Omega-3 fatty acids , Algae culture , Microalgae
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/6498 , vital:21097
- Description: Background and Aim: Microalgae are a potential economical source of omega-3 fatty acids, which are known for their health benefits. Omega-3 fatty acids derived from microalgae are however still expensive due to high costs involved in production. These costs can partly be attributed to cultivation of microalgae in unialgal cultures, which are prone to contamination, difficult to scale up and require stringent control of growth conditions. This study therefore is aimed to investigate the feasibility of using a mixed microalgae culture for the production of omega-3 fatty acids. Methods and materials: The microalgae were grown under uncontrolled conditions in a hanging-bag photo-bioreactor, with only the phosphorus-nitrogen ratio (P:N-ratio) varied. Variations in the different population proportions in the culture were studied and related to the biomass, total fatty acid and omega-3 fatty acid productivity of the culture. Finally, a comparison was made between the results obtained in this study and similar studies found in literature. Results and discussion: The mixed culture used was composed of several green microalgae, whose proportions varied with P:N-ratio, season, and age of the culture. Different interactions between the populations were observable, and these were thought to influence the culture’s biomass, total fatty acids (TFAs) and omega-3 fatty acid productivity. The TFA content of the culture was ~10-20% by the end of the exponential phase, depending on the nutrients supplied. The fatty acids were composed of mostly unsaturated fatty acids, the majority of which were omega-3 fatty acids; C18:3ω3 (up to 50% of TFA), C16:4ω3 (up to 15%) and C18:4ω3 (up to 5%). Other fatty acids observed included C16:0 (up to 25%), C18:1ω9/C18:1ω8 (up to 20%), C18:2ω6 (up to 5%), traces of C18:0, C18:3ω6, C17:0, C16:3ω3 and C16:1ω7 were also detected. The presence of these fatty acids was found to vary depending on season, P:N-ratio, and age of the culture. When compared to studies in the literature, the mixed culture was found to perform better than, or as well as reported studies, where unialgal cultures were cultivated under controlled laboratory conditions. Conclusion: In view of the reported advantages of cultivating mixed cultures, the production of omega-3 fatty acids via such cultures appears attractive. More research however is needed to optimise the culture; study interactions between the organisms and their effect on biomass, total fatty acid and omega-3 fatty acid productivity. Finally, the economic implications of using mixed cultures need to be evaluated as well.
- Full Text:
- Date Issued: 2013
Synthesis of fluorescent polymers with pendant triazole-substituted coumarin side-chains via a combination of click chemistry and raft-mediated polymerization
- Authors: Wali, Nwabisa Whitney
- Date: 2013
- Subjects: Fluorescent polymers , Polymerization , Macromolecules -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10432 , http://hdl.handle.net/10948/d1020142
- Description: This research project focuses on the synthesis of fluorescent polymers with pendant triazole-substituted coumarin side chain units. Copper(I)-catalyzed Huisgen’s 1,3-dipolar cycloaddition of alkynes with azides to form a 1,2,3-triazole ring, a typical example of “click” reaction, has been utilized for the synthesis of a novel vinyl monomer, 2-oxo-3-(4- vinyl-1H-1,2,3-triazol-1-yl)-2H-chromen-7-yl acetate 62. The monomer and its precursors were synthesised and characterized using 1D- and 2D-NMR and FT-IR. Coumarin-containing triazole polymers were synthesised using free radical polymerization. Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated polymerization was used to synthesise well defined coumarin-containing triazole polymers with moderate PDI values. The polymers were characterised using 1H-NMR and FT-IR. Modelling of the monomer precursor 61 and the monomer 62 at DFT level of approximation provided useful insights into possible conformations adopted by the monomer precursor 61 and the monomer 62. The photophysical properties of the novel monomer and the synthesised polymers were investigated in a polar solvent.
- Full Text:
- Date Issued: 2013
- Authors: Wali, Nwabisa Whitney
- Date: 2013
- Subjects: Fluorescent polymers , Polymerization , Macromolecules -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10432 , http://hdl.handle.net/10948/d1020142
- Description: This research project focuses on the synthesis of fluorescent polymers with pendant triazole-substituted coumarin side chain units. Copper(I)-catalyzed Huisgen’s 1,3-dipolar cycloaddition of alkynes with azides to form a 1,2,3-triazole ring, a typical example of “click” reaction, has been utilized for the synthesis of a novel vinyl monomer, 2-oxo-3-(4- vinyl-1H-1,2,3-triazol-1-yl)-2H-chromen-7-yl acetate 62. The monomer and its precursors were synthesised and characterized using 1D- and 2D-NMR and FT-IR. Coumarin-containing triazole polymers were synthesised using free radical polymerization. Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated polymerization was used to synthesise well defined coumarin-containing triazole polymers with moderate PDI values. The polymers were characterised using 1H-NMR and FT-IR. Modelling of the monomer precursor 61 and the monomer 62 at DFT level of approximation provided useful insights into possible conformations adopted by the monomer precursor 61 and the monomer 62. The photophysical properties of the novel monomer and the synthesised polymers were investigated in a polar solvent.
- Full Text:
- Date Issued: 2013