Statistical modelling applied to perceptions of fraud
- Authors: Mnci, Mihlali
- Date: 2017
- Subjects: Mathematical statistics Statistics , Mathematical models Bank fraud Banks and banking -- Security measures
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/41073 , vital:36289
- Description: This study aims to investigate and identify attitudes, behaviours and perceptions harboured by bank cardholders and merchants, which are associated with a higher susceptibility towards experiencing bank card fraud. Primary data was obtained from bank cardholders and merchants, from various business categories, in both the Nelson Mandela Bay Metropolitan Municipality and the City of Johannesburg Metropolitan Municipality. Following the use of parametric Multinomial Logistic Regression (MLR) and nonparametric conditional density estimation to analyse the data, the results are compared and relevant covariates/perceptions are determined from the more accurate of the two techniques. The results of the analysed survey data serve as a tool, highlighting areas which require further education and awareness on the part of merchants and bank clients.
- Full Text:
- Date Issued: 2017
- Authors: Mnci, Mihlali
- Date: 2017
- Subjects: Mathematical statistics Statistics , Mathematical models Bank fraud Banks and banking -- Security measures
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/41073 , vital:36289
- Description: This study aims to investigate and identify attitudes, behaviours and perceptions harboured by bank cardholders and merchants, which are associated with a higher susceptibility towards experiencing bank card fraud. Primary data was obtained from bank cardholders and merchants, from various business categories, in both the Nelson Mandela Bay Metropolitan Municipality and the City of Johannesburg Metropolitan Municipality. Following the use of parametric Multinomial Logistic Regression (MLR) and nonparametric conditional density estimation to analyse the data, the results are compared and relevant covariates/perceptions are determined from the more accurate of the two techniques. The results of the analysed survey data serve as a tool, highlighting areas which require further education and awareness on the part of merchants and bank clients.
- Full Text:
- Date Issued: 2017
Statistical modelling applied to perceptions of fraud
- Authors: Mnci, Mihlali
- Date: 2017
- Subjects: Mathematical statistics Statistics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/41064 , vital:36288
- Description: This study aims to investigate and identify attitudes, behaviours and perceptions harboured by bank cardholders and merchants, which are associated with a higher susceptibility towards experiencing bank card fraud. Primary data was obtained from bank cardholders and merchants, from various business categories, in both the Nelson Mandela Bay Metropolitan Municipality and the City of Johannesburg Metropolitan Municipality. Following the use of parametric Multinomial Logistic Regression (MLR) and nonparametric conditional density estimation to analyse the data, the results are compared and relevant covariates/perceptions are determined from the more accurate of the two techniques. The results of the analysed survey data serve as a tool, highlighting areas which require further education and awareness on the part of merchants and bank clients.
- Full Text:
- Date Issued: 2017
- Authors: Mnci, Mihlali
- Date: 2017
- Subjects: Mathematical statistics Statistics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/41064 , vital:36288
- Description: This study aims to investigate and identify attitudes, behaviours and perceptions harboured by bank cardholders and merchants, which are associated with a higher susceptibility towards experiencing bank card fraud. Primary data was obtained from bank cardholders and merchants, from various business categories, in both the Nelson Mandela Bay Metropolitan Municipality and the City of Johannesburg Metropolitan Municipality. Following the use of parametric Multinomial Logistic Regression (MLR) and nonparametric conditional density estimation to analyse the data, the results are compared and relevant covariates/perceptions are determined from the more accurate of the two techniques. The results of the analysed survey data serve as a tool, highlighting areas which require further education and awareness on the part of merchants and bank clients.
- Full Text:
- Date Issued: 2017
Statistical viability assessment of a photovoltaic system in the presence of data uncertainty
- Authors: Clohessy, Chantelle May
- Date: 2017
- Subjects: Bayesian field theory , Photovoltaic power systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/15655 , vital:28280
- Description: This thesis investigates statistical techniques that can be used to improve estimates and methods in feasibility assessments of photovoltaic (PV) systems. The use of these techniques are illustrated for a case study of a 1MW PV system proposed for the Nelson Mandela Metropolitan University South Campus in Port Elizabeth, South Africa. The results from the study provide strong support for the use of multivariate profile analysis and interval estimate plots for the assessment of solar resource data. A unique view to manufacturing process control in the generation of energy from a PV system is identified. This link between PV energy generation and process control is lacking in the literature and exploited in this study. Variance component models are used to model power output and energy yield estimates of the proposed PV system. The variance components are simulated using Bayesian simulation techniques. Bayesian tolerance intervals are derived from the variance components and are used to determine what percentage of future power output and energy yield values fall within an interval with a certain probability. The results from the estimated tolerance intervals were informative and provided expected power outputs and energy yields for a given month and specific season. The methods improve on current techniques used to assess the energy output of a system.
- Full Text:
- Date Issued: 2017
- Authors: Clohessy, Chantelle May
- Date: 2017
- Subjects: Bayesian field theory , Photovoltaic power systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/15655 , vital:28280
- Description: This thesis investigates statistical techniques that can be used to improve estimates and methods in feasibility assessments of photovoltaic (PV) systems. The use of these techniques are illustrated for a case study of a 1MW PV system proposed for the Nelson Mandela Metropolitan University South Campus in Port Elizabeth, South Africa. The results from the study provide strong support for the use of multivariate profile analysis and interval estimate plots for the assessment of solar resource data. A unique view to manufacturing process control in the generation of energy from a PV system is identified. This link between PV energy generation and process control is lacking in the literature and exploited in this study. Variance component models are used to model power output and energy yield estimates of the proposed PV system. The variance components are simulated using Bayesian simulation techniques. Bayesian tolerance intervals are derived from the variance components and are used to determine what percentage of future power output and energy yield values fall within an interval with a certain probability. The results from the estimated tolerance intervals were informative and provided expected power outputs and energy yields for a given month and specific season. The methods improve on current techniques used to assess the energy output of a system.
- Full Text:
- Date Issued: 2017
Studies on acoustic properties of non-woven fabrics
- Authors: Mvubu, Mlando Basel
- Date: 2017
- Subjects: Needlepunch (Nonwoven fabric) Nonwoven fabrics , Textile fabrics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/19387 , vital:28866
- Description: This study is divided in to two main parts. The first part deals with the optimization of process parameters of needle-punched non-woven fabrics for achieving maximum sound absorption by employing a Box-Behnken factorial design. The influence of fibre type, depth of needle penetration and stroke frequency on sound absorption properties were studied. These parameters were varied at three levels during experimental trials. From multiple regression analysis, it was observed that the depth of needle penetration alone was the most dominant factor among the selected parameters, which was followed by the interaction between depth of needle penetration and stroke frequency. Fibre type was the least dominant parameter affecting sound absorption. A maximum sound absorption coefficient of 47% (0.47) was obtained from the selected parameters. The results showed that for a process such as needle-punching, which is influenced by multiple variables, it is important to also study the interactive effects of process parameters for achieving optimum sound absorption. The second part of the study deals with the effect of type of natural fibre (fineness), and the blending ratio (with PET fibres) on the air permeability of the needle-punched non-woven fabrics and then it proceeds to study the effect of the air-gap, type of natural fibre (fineness) and blending ratio (with PET fibres) on sound absorption of needle-punched non-woven fabrics. These parameters are tested individually and their two way interaction (synergy) effect using ANOVA. The air-gap was varied from 0mm to 25mm with 5mm increments, three natural fibre types were used and all were blended with polyester fibres at three blending ratios for each natural fibre type. The Univariate Tests of Significance shows that all three parameters have a significant effect on sound absorption together with two two-way interactions, with the exception of the Blend Ratio × Air Gap two-way interaction which was not significant. It was found that the sound absorption improves with the increase in the air-gap size up to 15mm after which sound absorption decreased slightly with the further increase in the air-gap up to 25mm.
- Full Text:
- Date Issued: 2017
- Authors: Mvubu, Mlando Basel
- Date: 2017
- Subjects: Needlepunch (Nonwoven fabric) Nonwoven fabrics , Textile fabrics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/19387 , vital:28866
- Description: This study is divided in to two main parts. The first part deals with the optimization of process parameters of needle-punched non-woven fabrics for achieving maximum sound absorption by employing a Box-Behnken factorial design. The influence of fibre type, depth of needle penetration and stroke frequency on sound absorption properties were studied. These parameters were varied at three levels during experimental trials. From multiple regression analysis, it was observed that the depth of needle penetration alone was the most dominant factor among the selected parameters, which was followed by the interaction between depth of needle penetration and stroke frequency. Fibre type was the least dominant parameter affecting sound absorption. A maximum sound absorption coefficient of 47% (0.47) was obtained from the selected parameters. The results showed that for a process such as needle-punching, which is influenced by multiple variables, it is important to also study the interactive effects of process parameters for achieving optimum sound absorption. The second part of the study deals with the effect of type of natural fibre (fineness), and the blending ratio (with PET fibres) on the air permeability of the needle-punched non-woven fabrics and then it proceeds to study the effect of the air-gap, type of natural fibre (fineness) and blending ratio (with PET fibres) on sound absorption of needle-punched non-woven fabrics. These parameters are tested individually and their two way interaction (synergy) effect using ANOVA. The air-gap was varied from 0mm to 25mm with 5mm increments, three natural fibre types were used and all were blended with polyester fibres at three blending ratios for each natural fibre type. The Univariate Tests of Significance shows that all three parameters have a significant effect on sound absorption together with two two-way interactions, with the exception of the Blend Ratio × Air Gap two-way interaction which was not significant. It was found that the sound absorption improves with the increase in the air-gap size up to 15mm after which sound absorption decreased slightly with the further increase in the air-gap up to 25mm.
- Full Text:
- Date Issued: 2017
Synthesis and characterisation of lanthanide complexes with O,O-donor ligands: towards a new generation of hydrophosphonylation catalysts
- Authors: Mkwakwi, Kwakhanya
- Date: 2017
- Subjects: Rare earth metals Catalysts
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/11986 , vital:27016
- Description: This study investigates the coordination behaviour of potentially bi- and tridentate O,O- and O,N,O-donor Schiff base ligands with trivalent lanthanide ions. The reactions of lanthanide nitrates with 2-((E)-(tert-butylimino)methyl)-6-methoxyphenol (HL1) have yielded five complexes that are described by the general formula [Ln(HL1)2(NO3)3] (Ln = Ce, Nd, Gd, Ho and Er) and were characterised using physico-chemical techniques including single-crystal X-ray diffraction spectroscopy. The cerium complex crystallised in a triclinic (P-1) space group, while the rest of the complexes crystallised in the monoclinic (P21/c) space group. All the complexes are ten-coordinate adopting a tetradecahedron geometry with two HL1 molecules coordinated through the phenolic and methoxy oxygen atoms. The coordination sphere is completed by six oxygen atoms from three bidentately coordinated nitrate ligands. Electronic data reveals that only the neodymium, holmium and erbium complexes exhibit weak f-f transitions in the visible region. The redox behaviour of the complexes was also investigated and reported. Five novel complexes were prepared by reacting 2-((E)-(tert-butylimino)methyl)phenol (HL2) with [Ln(NO3)3∙xH2O] (Ln = Gd and Dy ; x = 5 or 6) and [LnCl3∙6H2O] (Ln = Nd, Gd and Dy). The crystal structures of the former two complexes are isostructural and the coordination sphere is composed of three HL2 ligands bonded to the metal centre through the phenolic oxygen atom and three nitrate ions coordinated in a bidentate fashion. Both complexes are nine-coordinate and SHAPE analysis reveals that they adopted a muffin geometry. The average Ln-Onitrate and Ln-Ophenolate bond lengths are 2.5078 and 2.2814 Å, respectively. The complexes derived from the chloride salts exhibited an octahedral geometry with four monodentate ligands [Ln-Ophenolate distances range from 2.224(4) to 2.2797(17) Å] coordinating in the equatorial positions and two chloride ions [average Ln-Cl bond length is 2.6527 Å, and average Cl-Ln-Cl angles is 180o] in axial positions. The ligand coordinated through the phenolic oxygen with the phenolic proton migrating to the imino nitrogen to give a zwitterionic form of the ligand. There are weak C-H∙∙∙Cl interactions present and O-H∙∙∙N hydrogen bonds are also observed in the crystal packing. The synthesis of lanthanide complexes with methoxy-6-((E)-(phenylimino)methyl)phenol (HL3) was carried out in methanol to yield two mononuclear complexes with the formulae [Nd(HL3)2(NO3)3] and [Ho(HL3)(NO3)3(DMF)(H2O)]. Single-crystal crystallographic studies shows that the neodymium complex contains two HL3 ligands coordinated bidentately through its methoxide and phenolic oxygen atoms, with three nitrate ions also bonded to the metal in a bidentate manner. The coordination geometry in the holmium complex is composed of only oxygen atoms from the various ligands. Both complexes are ten-coordinate and exhibit a tetradecahedron geometry.
- Full Text:
- Date Issued: 2017
- Authors: Mkwakwi, Kwakhanya
- Date: 2017
- Subjects: Rare earth metals Catalysts
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/11986 , vital:27016
- Description: This study investigates the coordination behaviour of potentially bi- and tridentate O,O- and O,N,O-donor Schiff base ligands with trivalent lanthanide ions. The reactions of lanthanide nitrates with 2-((E)-(tert-butylimino)methyl)-6-methoxyphenol (HL1) have yielded five complexes that are described by the general formula [Ln(HL1)2(NO3)3] (Ln = Ce, Nd, Gd, Ho and Er) and were characterised using physico-chemical techniques including single-crystal X-ray diffraction spectroscopy. The cerium complex crystallised in a triclinic (P-1) space group, while the rest of the complexes crystallised in the monoclinic (P21/c) space group. All the complexes are ten-coordinate adopting a tetradecahedron geometry with two HL1 molecules coordinated through the phenolic and methoxy oxygen atoms. The coordination sphere is completed by six oxygen atoms from three bidentately coordinated nitrate ligands. Electronic data reveals that only the neodymium, holmium and erbium complexes exhibit weak f-f transitions in the visible region. The redox behaviour of the complexes was also investigated and reported. Five novel complexes were prepared by reacting 2-((E)-(tert-butylimino)methyl)phenol (HL2) with [Ln(NO3)3∙xH2O] (Ln = Gd and Dy ; x = 5 or 6) and [LnCl3∙6H2O] (Ln = Nd, Gd and Dy). The crystal structures of the former two complexes are isostructural and the coordination sphere is composed of three HL2 ligands bonded to the metal centre through the phenolic oxygen atom and three nitrate ions coordinated in a bidentate fashion. Both complexes are nine-coordinate and SHAPE analysis reveals that they adopted a muffin geometry. The average Ln-Onitrate and Ln-Ophenolate bond lengths are 2.5078 and 2.2814 Å, respectively. The complexes derived from the chloride salts exhibited an octahedral geometry with four monodentate ligands [Ln-Ophenolate distances range from 2.224(4) to 2.2797(17) Å] coordinating in the equatorial positions and two chloride ions [average Ln-Cl bond length is 2.6527 Å, and average Cl-Ln-Cl angles is 180o] in axial positions. The ligand coordinated through the phenolic oxygen with the phenolic proton migrating to the imino nitrogen to give a zwitterionic form of the ligand. There are weak C-H∙∙∙Cl interactions present and O-H∙∙∙N hydrogen bonds are also observed in the crystal packing. The synthesis of lanthanide complexes with methoxy-6-((E)-(phenylimino)methyl)phenol (HL3) was carried out in methanol to yield two mononuclear complexes with the formulae [Nd(HL3)2(NO3)3] and [Ho(HL3)(NO3)3(DMF)(H2O)]. Single-crystal crystallographic studies shows that the neodymium complex contains two HL3 ligands coordinated bidentately through its methoxide and phenolic oxygen atoms, with three nitrate ions also bonded to the metal in a bidentate manner. The coordination geometry in the holmium complex is composed of only oxygen atoms from the various ligands. Both complexes are ten-coordinate and exhibit a tetradecahedron geometry.
- Full Text:
- Date Issued: 2017
Synthesis and investigation of the chemosensing properties of novel fluorescent triazolyl coumarin-based polymers
- Ngororabanga, Jean Marie Vianney
- Authors: Ngororabanga, Jean Marie Vianney
- Date: 2017
- Subjects: Fluorescent polymers Chemical detectors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/20110 , vital:29120
- Description: Environmental pollution by ionic species has become one of the greatest challenges to the sustainable development of communities. Increasing amounts of these ionic species in the environment is associated with several detrimental effects to human health and ecological systems. Proper detection and monitoring of these ionic species is essential. Considering the diversity of the ions and the fact that the available sensors are limited, it is clear that there is need for a rapid and low-cost method for recognition and monitoring of these ions. Fluorescence based methods are ranked among the most powerful transduction systems to signal chemical recognition events. Fluorescent polymers containing triazolyl coumarin units in the polymer backbone or as pendant groups were therefore designed and investigated as potential sensors for these ions. Three methods were used to incorporate triazolyl coumarin units into the polymers. The first method involved polymerization of the vinyl monomer containing the triazolyl coumarin unit. The second method involved AA-BB step-grow click polymerization of diazide and dialkyne-functionalized monomers. The third method involved post-polymerization functionalization of an azide-functionalized polymer with an alkyne functionalized coumarin derivative. In each method, formation of the triazole ring was achieved using a Cu(I)-catalyzed 1,3-dipolar cycloaddition (CuAAC) reaction. The photophysical properties of the polymers and their starting monomers were investigated and compared. Polymers with triazolyl coumarin units in the backbone or as pendant groups were found to have higher absorption and emission intensities than their corresponding monomers while polymers resulting from functionalization of azide-functionalized polymer were found to exhibit improved photophysical properties compared to the starting azide-functionalized polymer. The chemosensing potential of the polymers was investigated through absorption and emission. The polymers were found to be selective towards different metal ions (Fe3+, Hg2+ and Al3+) and anions (-OH and F-). The mechanisms of interaction between the polymers and ions were investigated by comparing the absorption and emission spectra of the polymers to those of their monomers in the presence of an ion of interest. In some cases the mechanism of interaction was supported by 1H NMR and FT-IR.
- Full Text:
- Date Issued: 2017
- Authors: Ngororabanga, Jean Marie Vianney
- Date: 2017
- Subjects: Fluorescent polymers Chemical detectors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/20110 , vital:29120
- Description: Environmental pollution by ionic species has become one of the greatest challenges to the sustainable development of communities. Increasing amounts of these ionic species in the environment is associated with several detrimental effects to human health and ecological systems. Proper detection and monitoring of these ionic species is essential. Considering the diversity of the ions and the fact that the available sensors are limited, it is clear that there is need for a rapid and low-cost method for recognition and monitoring of these ions. Fluorescence based methods are ranked among the most powerful transduction systems to signal chemical recognition events. Fluorescent polymers containing triazolyl coumarin units in the polymer backbone or as pendant groups were therefore designed and investigated as potential sensors for these ions. Three methods were used to incorporate triazolyl coumarin units into the polymers. The first method involved polymerization of the vinyl monomer containing the triazolyl coumarin unit. The second method involved AA-BB step-grow click polymerization of diazide and dialkyne-functionalized monomers. The third method involved post-polymerization functionalization of an azide-functionalized polymer with an alkyne functionalized coumarin derivative. In each method, formation of the triazole ring was achieved using a Cu(I)-catalyzed 1,3-dipolar cycloaddition (CuAAC) reaction. The photophysical properties of the polymers and their starting monomers were investigated and compared. Polymers with triazolyl coumarin units in the backbone or as pendant groups were found to have higher absorption and emission intensities than their corresponding monomers while polymers resulting from functionalization of azide-functionalized polymer were found to exhibit improved photophysical properties compared to the starting azide-functionalized polymer. The chemosensing potential of the polymers was investigated through absorption and emission. The polymers were found to be selective towards different metal ions (Fe3+, Hg2+ and Al3+) and anions (-OH and F-). The mechanisms of interaction between the polymers and ions were investigated by comparing the absorption and emission spectra of the polymers to those of their monomers in the presence of an ion of interest. In some cases the mechanism of interaction was supported by 1H NMR and FT-IR.
- Full Text:
- Date Issued: 2017
Synthesis of L-menthyl glyoxylate, an important intermediate in the manufacture of ARVS, using flow chemistry technology
- Authors: Moyo, McQuillan
- Date: 2017
- Subjects: Chemistry , Pharmaceutical chemistry , Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/12019 , vital:27018
- Description: Herein an alternative approach to the conventional batch synthesis of L-menthyl glyoxylate hydrate (MGH), an important intermediate in the synthesis of drugs of importance is reported, through flow chemistry technology. MGH was initially synthesized in batch and various reaction parameters optimized. It was found to proceed to completion after 6 hours of esterifying glyoxylic acid with excess alcohol (L-menthol) in the presence of a catalyst, ideally amberlyst-15 (an ion exchange resin) at 105 °C giving a yield of 72 %. The batch reaction conditions were adopted in a continuous flow synthesis setup, using the Labtrix Start system, in which reaction conditions were optimized. The optimization of glyoxylic acid conversion (92 %) in the Labtrix Start system gave reaction conditions that resulted in low MGH selectivity (25 %) whereas the optimization for MGH selectivity (100 %) gave a conversion a poor glyoxylic acid conversion (15 %). The FlowSyn system fitted with a column reactor gave the best results, in which the optimum conditions were an excess of L-menthol (1.5 M, 6.0 equiv.), temperature (80 °C) and a residence time of 2.5 minutes with a high selectivity (77 %) and average conversion (50 %). The optimized reaction conditions for conversion and selectivity on the different flow systems did not vary significantly and similar trends were observed for the systems. It was shown that an increase in temperature, mole equivalents and residence time led to an increase in MGH conversion in all flow systems. The scale up of the esterification reaction from the Labtrix Start system (19 μL microreactor) to the FlowSyn system fitted with a 2 mL reactor chip, showed that the reaction proceeds with a slight drop in selectivity from 100 % to 92 % while conversion dropped from 15 to 12 %. On the contrary, a significant drop in conversion and selectivity were observed when the FlowSyn column reactor was up-scaled to the Elite-tubular furnace, owing to the poor mixing in the larger channel size reactor.
- Full Text:
- Date Issued: 2017
- Authors: Moyo, McQuillan
- Date: 2017
- Subjects: Chemistry , Pharmaceutical chemistry , Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/12019 , vital:27018
- Description: Herein an alternative approach to the conventional batch synthesis of L-menthyl glyoxylate hydrate (MGH), an important intermediate in the synthesis of drugs of importance is reported, through flow chemistry technology. MGH was initially synthesized in batch and various reaction parameters optimized. It was found to proceed to completion after 6 hours of esterifying glyoxylic acid with excess alcohol (L-menthol) in the presence of a catalyst, ideally amberlyst-15 (an ion exchange resin) at 105 °C giving a yield of 72 %. The batch reaction conditions were adopted in a continuous flow synthesis setup, using the Labtrix Start system, in which reaction conditions were optimized. The optimization of glyoxylic acid conversion (92 %) in the Labtrix Start system gave reaction conditions that resulted in low MGH selectivity (25 %) whereas the optimization for MGH selectivity (100 %) gave a conversion a poor glyoxylic acid conversion (15 %). The FlowSyn system fitted with a column reactor gave the best results, in which the optimum conditions were an excess of L-menthol (1.5 M, 6.0 equiv.), temperature (80 °C) and a residence time of 2.5 minutes with a high selectivity (77 %) and average conversion (50 %). The optimized reaction conditions for conversion and selectivity on the different flow systems did not vary significantly and similar trends were observed for the systems. It was shown that an increase in temperature, mole equivalents and residence time led to an increase in MGH conversion in all flow systems. The scale up of the esterification reaction from the Labtrix Start system (19 μL microreactor) to the FlowSyn system fitted with a 2 mL reactor chip, showed that the reaction proceeds with a slight drop in selectivity from 100 % to 92 % while conversion dropped from 15 to 12 %. On the contrary, a significant drop in conversion and selectivity were observed when the FlowSyn column reactor was up-scaled to the Elite-tubular furnace, owing to the poor mixing in the larger channel size reactor.
- Full Text:
- Date Issued: 2017
Synthesis, crystal structures and molecular modelling of rare earth complexes with bis(2-pyridylmethyl)amine: aim topological analysis and ligand conformation search
- Authors: Matthews, Cameron
- Date: 2017
- Subjects: Rare earths , Ligands , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8230 , vital:26229
- Description: Eight rare earth complexes with bis(2-pyridylmethyl)amine (DPA) were synthesised and recrystallised, under air-sensitive or low moisture conditions. The crystal structures were successfully determined, via SC-XRD, and the asymmetric units of five complexes (1, 3, 5, 6 and 7) were submitted for DFT molecular modelling calculations, which involved geometry optimisation and frequency calculations. The neutral complexes obtained were bis(bis(2-pyridylmethyl)amine)-trichloro-lanthanum(III) [LaCl3(DPA)2] (1), bis(bis(2-pyridylmethyl)amine)-trichloro-cerium(III)) [CeCl3(DPA)2] (2), bis(μ2-chloro)-diaqua-tetrachloro-bis(bis(2-pyridylmethyl)amine)-di-praseodymium(III) [PrCl2(μ-Cl)(DPA)(OH2)]2 (3) and bis(μ2-methoxo)-bis(bis(2-pyridylmethyl)amine)- tetrachloro-di-dysprosium(III) [DyCl2(μ-OCH3)(DPA)]2 (4). The cationic complexes obtained in this study were dichloro-bis(bis(2-pyridylmethyl)amine)- neodymium(III) chloride methanol solvate [NdCl2(DPA)2]Cl·CH3OH (5), dichloro-bis(bis(2- pyridylmethyl)amine)-dysprosium(III) chloride methanol solvate [DyCl2(DPA)2]Cl·CH3OH (6), dichloro-bis(bis(2-pyridylmethyl)amine)-yttrium(III) chloride methanol solvate [YCl2(DPA)2]Cl·CH3OH (7) and dichloro-bis(bis(2-pyridylmethyl)amine)-lutetium(III) chloride methanol solvate [LuCl2(DPA)2]Cl·CH3OH (8). The ‘Quantum theory of atoms in molecules’ approach was used to investigate the electron density topology, primarily in order to investigate the hydrogen and coordination bonds for three of the eight complexes. Two of the neutral complexes contain the ‘early’ rare earth elements lanthanum and praseodymium and one cationic complex contains the ‘late’ lanthanide element dysprosium. Noncovalent interaction analysis was also performed on the aforementioned complexes in order to gain a deeper understanding of the intra-molecular stereo-electronic interactions. Spin density analysis was used to investigate the distribution of unpaired electron density at and around the metal centres of the aforementioned paramagnetic Pr- and Dy-complexes. A ligand conformation search for DPA was undertaken and 32 low energy conformers were identified and their relative energies were determined using two DFT functionals, namely M06 and M06-2X.
- Full Text:
- Date Issued: 2017
- Authors: Matthews, Cameron
- Date: 2017
- Subjects: Rare earths , Ligands , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8230 , vital:26229
- Description: Eight rare earth complexes with bis(2-pyridylmethyl)amine (DPA) were synthesised and recrystallised, under air-sensitive or low moisture conditions. The crystal structures were successfully determined, via SC-XRD, and the asymmetric units of five complexes (1, 3, 5, 6 and 7) were submitted for DFT molecular modelling calculations, which involved geometry optimisation and frequency calculations. The neutral complexes obtained were bis(bis(2-pyridylmethyl)amine)-trichloro-lanthanum(III) [LaCl3(DPA)2] (1), bis(bis(2-pyridylmethyl)amine)-trichloro-cerium(III)) [CeCl3(DPA)2] (2), bis(μ2-chloro)-diaqua-tetrachloro-bis(bis(2-pyridylmethyl)amine)-di-praseodymium(III) [PrCl2(μ-Cl)(DPA)(OH2)]2 (3) and bis(μ2-methoxo)-bis(bis(2-pyridylmethyl)amine)- tetrachloro-di-dysprosium(III) [DyCl2(μ-OCH3)(DPA)]2 (4). The cationic complexes obtained in this study were dichloro-bis(bis(2-pyridylmethyl)amine)- neodymium(III) chloride methanol solvate [NdCl2(DPA)2]Cl·CH3OH (5), dichloro-bis(bis(2- pyridylmethyl)amine)-dysprosium(III) chloride methanol solvate [DyCl2(DPA)2]Cl·CH3OH (6), dichloro-bis(bis(2-pyridylmethyl)amine)-yttrium(III) chloride methanol solvate [YCl2(DPA)2]Cl·CH3OH (7) and dichloro-bis(bis(2-pyridylmethyl)amine)-lutetium(III) chloride methanol solvate [LuCl2(DPA)2]Cl·CH3OH (8). The ‘Quantum theory of atoms in molecules’ approach was used to investigate the electron density topology, primarily in order to investigate the hydrogen and coordination bonds for three of the eight complexes. Two of the neutral complexes contain the ‘early’ rare earth elements lanthanum and praseodymium and one cationic complex contains the ‘late’ lanthanide element dysprosium. Noncovalent interaction analysis was also performed on the aforementioned complexes in order to gain a deeper understanding of the intra-molecular stereo-electronic interactions. Spin density analysis was used to investigate the distribution of unpaired electron density at and around the metal centres of the aforementioned paramagnetic Pr- and Dy-complexes. A ligand conformation search for DPA was undertaken and 32 low energy conformers were identified and their relative energies were determined using two DFT functionals, namely M06 and M06-2X.
- Full Text:
- Date Issued: 2017
The Aardvark as an ecological engineer in the Eastern Karoo: dig patterns and emergent processes
- Martin, Stephanie Ann, Landman, Marietjie
- Authors: Martin, Stephanie Ann , Landman, Marietjie
- Date: 2017
- Subjects: Ecosystem services -- South Africa -- Eastern Cape Environmental engineering -- South Africa -- Eastern Cape Soil dynamics -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/11952 , vital:27010
- Description: Species which play particularly important roles in ecosystem patterns and processes are recognised as keystone species or ecosystem engineers. The conservation of these species is critical for the maintenance of the ecological role they play in ecosystem function. The aardvark, Orycteropus afer, is known to play a role in biopedturbation through digging for refuges and for prey, and as a consequence of these digging activities is expected to serve the role of an ecosystem engineer and keystone species. This study aimed to describe and quantify the ecological patterns and processes driven by the aardvark through their digging activities, within the eastern Karoo, and thereby evaluate the significance of aardvarks as ecosystem engineers and keystone species in a semi-arid environment. The landscape pattern (dig abundance and distribution) and soil displacement of aardvark forage and refuge digs in a semi-arid Karoo landscape, as well as the ecological processes (generating fertile, seed retention hotspots) driven by aardvark forage digs was measured. Refuge digs occurred in the highest densities in areas characterised by a specific suite of soil, vegetation and elevation features, while forage digs occurred in high abundance in most habitats measured, and were likely driven by prey availability. Forage digs served as litter and seed retention hotspots, with accelerated decomposition rates of litter as a function of increased soil moisture in digs. The functional processes (i.e. resource capture, shelter for plants and animals, germination sites, soil aeration, organic turnover, mineralization rates, fertile soil displacement and transport) driven by aardvark digs are not restricted to refuge digs. Forage digs occurred in most habitats measured and their functional role is unique and perhaps greater across the landscape in comparison to refuge digs. The aardvark has a disproportionate effect in ecosystems, in terms of its refuge and forage digs relative to its abundance and therefore its role as a keystone species and ecosystem engineer is confirmed. Conservation and protection of this species is therefore essential to maintain its important role in ecosystem function.
- Full Text:
- Date Issued: 2017
- Authors: Martin, Stephanie Ann , Landman, Marietjie
- Date: 2017
- Subjects: Ecosystem services -- South Africa -- Eastern Cape Environmental engineering -- South Africa -- Eastern Cape Soil dynamics -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/11952 , vital:27010
- Description: Species which play particularly important roles in ecosystem patterns and processes are recognised as keystone species or ecosystem engineers. The conservation of these species is critical for the maintenance of the ecological role they play in ecosystem function. The aardvark, Orycteropus afer, is known to play a role in biopedturbation through digging for refuges and for prey, and as a consequence of these digging activities is expected to serve the role of an ecosystem engineer and keystone species. This study aimed to describe and quantify the ecological patterns and processes driven by the aardvark through their digging activities, within the eastern Karoo, and thereby evaluate the significance of aardvarks as ecosystem engineers and keystone species in a semi-arid environment. The landscape pattern (dig abundance and distribution) and soil displacement of aardvark forage and refuge digs in a semi-arid Karoo landscape, as well as the ecological processes (generating fertile, seed retention hotspots) driven by aardvark forage digs was measured. Refuge digs occurred in the highest densities in areas characterised by a specific suite of soil, vegetation and elevation features, while forage digs occurred in high abundance in most habitats measured, and were likely driven by prey availability. Forage digs served as litter and seed retention hotspots, with accelerated decomposition rates of litter as a function of increased soil moisture in digs. The functional processes (i.e. resource capture, shelter for plants and animals, germination sites, soil aeration, organic turnover, mineralization rates, fertile soil displacement and transport) driven by aardvark digs are not restricted to refuge digs. Forage digs occurred in most habitats measured and their functional role is unique and perhaps greater across the landscape in comparison to refuge digs. The aardvark has a disproportionate effect in ecosystems, in terms of its refuge and forage digs relative to its abundance and therefore its role as a keystone species and ecosystem engineer is confirmed. Conservation and protection of this species is therefore essential to maintain its important role in ecosystem function.
- Full Text:
- Date Issued: 2017
The action of sutherlandia frutescens on macrophage differentiation & function
- Authors: Camille, Ned
- Date: 2017
- Subjects: Medicinal plants Macrophages
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/22112 , vital:29841
- Description: Sutherlandia frutescens (S. frutescens) is a medicinal plant, indigenous to South Africa used to treat various conditions, including Type II Diabetes (T2D) and immune disorders. Many of these conditions involve the macrophage lineage in low grade chronic inflammation, characterized by elevated pro-inflammatory cytokines. The macrophage population can be divided into pro-inflammatory (M1) and anti-inflammatory (M2) sub-populations. S. frutescens is believed to possess the potential to regulate macrophage differentiation and metabolic immune diseases. This makes it important to investigate its molecular action to determine its potential ethnopharmacological use. The aims of this study were to explore the role of S. frutescens on M1/M2 macrophage function, using extracts prepared from a single plant source previously shown to target T2D, and to determine its potential mechanistic pathways using the murine macrophage-like RAW 264.7 cell line. The action of a hot aqueous and a 100% ethanolic extract of S. frutescens were tested in the RAW 264.7 cell line following Lipopolysaccharide (LPS) induction. The effect of these extracts on activation of a pro-inflammatory M1 phenotype and an anti-inflammatory M2 phenotype was investigated by flow cytometry using the CD markers CD86 (M1) and CD206 (M2). M1 macrophage pro-inflammatory responses were measured by production of nitric oxide (NO) using the Griess reagent and reactive oxygen species (ROS) production and cyclooxygenase 2 (COX-2) expression by flow cytometry. Cytokine production was quantified by ELISA assays. Toll-like receptor-4 (TLR4), inducible nitric oxide synthase (iNOS) (M1) and Heme-oxygenase 1 (HMOX-1) (M2) mRNA expression were quantified by quantitative reverse transcription polymerase chain reaction (RT-qPCR). Arginase-1 activity (M2) was measured by the urea assay. The effect of S. frutescens extracts on nuclear factor kappa-light-chain-enhancer of activated B-cells (NF-κB) and mitogen activated protein kinases (MAPK) signaling pathway were determined with flow cytometry and Image Express XLS microscopy. After 24 hour treatment, both the hot aqueous and ethanolic extracts of S. frutescens significantly inhibited all M1 functions, and altered the pattern of CD expression from M1 (CD86+) to M2 (CD206+) in RAW 264.7 cells following activation by LPS, with the ethanolic extract having the greatest activity. M1-type cytokines were downregulated, while the M2 cytokine profile remained unchanged. S. frutescens was shown to mediate its action through suppression of both NF-κB and MAPK pathways and not through HMOX-1, exerting most activity through decreased p38 MAPK phosphorylation. We show that S. frutescens aids in the potential reversal of imbalances in the macrophage M1 and M2 sub-populations, leading to amelioration of disease. We hypothesize that regulation occurs during the differentiation and activation processes, with reduction in inflammation and direction towards M2 anti-inflammatory activity. This could promote tissue remodeling and immune regulation and has potential to alleviate the pathogenesis of both T2D and immune diseases.
- Full Text:
- Date Issued: 2017
- Authors: Camille, Ned
- Date: 2017
- Subjects: Medicinal plants Macrophages
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/22112 , vital:29841
- Description: Sutherlandia frutescens (S. frutescens) is a medicinal plant, indigenous to South Africa used to treat various conditions, including Type II Diabetes (T2D) and immune disorders. Many of these conditions involve the macrophage lineage in low grade chronic inflammation, characterized by elevated pro-inflammatory cytokines. The macrophage population can be divided into pro-inflammatory (M1) and anti-inflammatory (M2) sub-populations. S. frutescens is believed to possess the potential to regulate macrophage differentiation and metabolic immune diseases. This makes it important to investigate its molecular action to determine its potential ethnopharmacological use. The aims of this study were to explore the role of S. frutescens on M1/M2 macrophage function, using extracts prepared from a single plant source previously shown to target T2D, and to determine its potential mechanistic pathways using the murine macrophage-like RAW 264.7 cell line. The action of a hot aqueous and a 100% ethanolic extract of S. frutescens were tested in the RAW 264.7 cell line following Lipopolysaccharide (LPS) induction. The effect of these extracts on activation of a pro-inflammatory M1 phenotype and an anti-inflammatory M2 phenotype was investigated by flow cytometry using the CD markers CD86 (M1) and CD206 (M2). M1 macrophage pro-inflammatory responses were measured by production of nitric oxide (NO) using the Griess reagent and reactive oxygen species (ROS) production and cyclooxygenase 2 (COX-2) expression by flow cytometry. Cytokine production was quantified by ELISA assays. Toll-like receptor-4 (TLR4), inducible nitric oxide synthase (iNOS) (M1) and Heme-oxygenase 1 (HMOX-1) (M2) mRNA expression were quantified by quantitative reverse transcription polymerase chain reaction (RT-qPCR). Arginase-1 activity (M2) was measured by the urea assay. The effect of S. frutescens extracts on nuclear factor kappa-light-chain-enhancer of activated B-cells (NF-κB) and mitogen activated protein kinases (MAPK) signaling pathway were determined with flow cytometry and Image Express XLS microscopy. After 24 hour treatment, both the hot aqueous and ethanolic extracts of S. frutescens significantly inhibited all M1 functions, and altered the pattern of CD expression from M1 (CD86+) to M2 (CD206+) in RAW 264.7 cells following activation by LPS, with the ethanolic extract having the greatest activity. M1-type cytokines were downregulated, while the M2 cytokine profile remained unchanged. S. frutescens was shown to mediate its action through suppression of both NF-κB and MAPK pathways and not through HMOX-1, exerting most activity through decreased p38 MAPK phosphorylation. We show that S. frutescens aids in the potential reversal of imbalances in the macrophage M1 and M2 sub-populations, leading to amelioration of disease. We hypothesize that regulation occurs during the differentiation and activation processes, with reduction in inflammation and direction towards M2 anti-inflammatory activity. This could promote tissue remodeling and immune regulation and has potential to alleviate the pathogenesis of both T2D and immune diseases.
- Full Text:
- Date Issued: 2017
The design and testing of a national estuarine monitoring prgramme for South Africa
- Authors: Cilliers, Gerhard Jordaan
- Date: 2017
- Subjects: Estuaries -- South Africa Berg Estuary (South Africa)
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/15490 , vital:28258
- Description: Adaptive water resource management requires sound scientific based decisions, emanating from robust scientific data. The Department of Environmental Affairs are mandated for collaborative management of the South African coast, including estuaries, through the Integrated Coastal Management Act (Act no 24 of 2008) (ICMA). The Department Water and Sanitation is mandated through the National Water Act (Act no 36 of 1998) (NWA) to design, test and implement monitoring programmes to provide water resource data. Extensive freshwater monitoring programmes exist in South Africa but there is no standard long-term monitoring programme for estuaries. This study designed and tested a National Estuarine Monitoring Programme (NESMP) that is anchored in the NWA and the ICMA. The design was based on a review of international estuary monitoring programmes, consultation with relevant role players and five decades experience in the design, testing and implementation of water resource monitoring programmes by DWS. The main objective of this thesis is 1) to design a national estuarine monitoring programme 2) test the design of the programme for practical implementation by reflecting on collected data from case studies, and 3) design a Decision Support System to translate complex monitoring data into management information. The main objective of the NESMP is 1) to collect long-term data to determine trends in the condition of estuaries in South Africa and 2) to provide management orientated information for effective estuary management. The National Estuary Monitoring programme consists of three tiers. Tier 1 focuses on basic data including system variables and nutrient data. Tier 2 collects data required for the determination of the Ecological Water Requirements (EWR) of estuaries in accordance with a standardised method used by DWS. A tailor made monitoring programme addressing specific issues including pollution incidents and localised development pressure, making use of a combination of Tier 1 and Tier 2 components, forms Tier 3 of the NESMP. This study tested the Tier 1 components of the programme on 28 estuaries across the South African coast since 2012. However, due to space constraints, the data reflected on in this thesis, is only for case studies on the Berg and Breede estuaries between 2012 and 2016. The results indicate that the establishment and operation of the NESMP on South African estuaries making use of monthly surveys, and the deployment of permanent water quality loggers, in line with the proposed protocol, are possible. This does however require collaboration with other role players in order to share responsibility and associated resources. A tiered management structure ensures national, regional and local level implementation takes place seamlessly. A decision support system (DSS) was also designed as part of this thesis to assist with data interpretation and the creation of management orientated information. This DSS includes a measurement of the percentage exceedance of the Threshold of Potential Concern (TPC), which acts as an early warning system for water resource deterioration. This study showed that effective collaboration will ensure the sustainability of the NESMP. Implementation of the more complex and resource intensive Tier 2 and Tier 3 sampling will however need to be investigated to establish the overall success of the NESMP.
- Full Text:
- Date Issued: 2017
- Authors: Cilliers, Gerhard Jordaan
- Date: 2017
- Subjects: Estuaries -- South Africa Berg Estuary (South Africa)
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/15490 , vital:28258
- Description: Adaptive water resource management requires sound scientific based decisions, emanating from robust scientific data. The Department of Environmental Affairs are mandated for collaborative management of the South African coast, including estuaries, through the Integrated Coastal Management Act (Act no 24 of 2008) (ICMA). The Department Water and Sanitation is mandated through the National Water Act (Act no 36 of 1998) (NWA) to design, test and implement monitoring programmes to provide water resource data. Extensive freshwater monitoring programmes exist in South Africa but there is no standard long-term monitoring programme for estuaries. This study designed and tested a National Estuarine Monitoring Programme (NESMP) that is anchored in the NWA and the ICMA. The design was based on a review of international estuary monitoring programmes, consultation with relevant role players and five decades experience in the design, testing and implementation of water resource monitoring programmes by DWS. The main objective of this thesis is 1) to design a national estuarine monitoring programme 2) test the design of the programme for practical implementation by reflecting on collected data from case studies, and 3) design a Decision Support System to translate complex monitoring data into management information. The main objective of the NESMP is 1) to collect long-term data to determine trends in the condition of estuaries in South Africa and 2) to provide management orientated information for effective estuary management. The National Estuary Monitoring programme consists of three tiers. Tier 1 focuses on basic data including system variables and nutrient data. Tier 2 collects data required for the determination of the Ecological Water Requirements (EWR) of estuaries in accordance with a standardised method used by DWS. A tailor made monitoring programme addressing specific issues including pollution incidents and localised development pressure, making use of a combination of Tier 1 and Tier 2 components, forms Tier 3 of the NESMP. This study tested the Tier 1 components of the programme on 28 estuaries across the South African coast since 2012. However, due to space constraints, the data reflected on in this thesis, is only for case studies on the Berg and Breede estuaries between 2012 and 2016. The results indicate that the establishment and operation of the NESMP on South African estuaries making use of monthly surveys, and the deployment of permanent water quality loggers, in line with the proposed protocol, are possible. This does however require collaboration with other role players in order to share responsibility and associated resources. A tiered management structure ensures national, regional and local level implementation takes place seamlessly. A decision support system (DSS) was also designed as part of this thesis to assist with data interpretation and the creation of management orientated information. This DSS includes a measurement of the percentage exceedance of the Threshold of Potential Concern (TPC), which acts as an early warning system for water resource deterioration. This study showed that effective collaboration will ensure the sustainability of the NESMP. Implementation of the more complex and resource intensive Tier 2 and Tier 3 sampling will however need to be investigated to establish the overall success of the NESMP.
- Full Text:
- Date Issued: 2017
The effect of synthetically-derived xanthone compounds on the suppression of the progression of breast cancer and the associated complications
- Authors: Davison, Candace
- Date: 2017
- Subjects: Breast -- Cancer -- Chemotherapy Breast -- Cancer -- Prevention , Antibacterial agents -- Therapeutic use
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/13889 , vital:27354
- Description: Breast cancer is the most frequently diagnosed cancer in women worldwide.A treatment regime, both effective and safe and can only be achieved once more effective chemotherapeutic agents are discovered or identified. These “drugs” must selectively induce cell death such as apoptosis or necroptosis in the cancer cells. Apoptotic cell death allows a cell to “commit suicide” in genetically- controlled or programmed mechanism(s). The microenvironment of the tumour is important since a nurturing malignant environment is required for tumour maintenance, progression and ultimately the development of metastasis. Due to the correlation of the tumour microenvironment to aggressive tumour progression, emphasis should be placed on the constituents of the tumour’s microenvironment. In recent years, the understanding of intracellular pathways in cancer cells has increased rapidly, contributing to the development of drugs with more specific targets such as growth factors, signalling molecules, cell adhesion proteins, proteases, cell-cycle proteins, modulators of apoptosis and molecules that promote angiogenesis and metastasis. The main aim of this study was thus to identify a few potential or active compounds from a library of synthetically-derived compounds as possible alternative breast cancer treatment candidates.
- Full Text:
- Date Issued: 2017
- Authors: Davison, Candace
- Date: 2017
- Subjects: Breast -- Cancer -- Chemotherapy Breast -- Cancer -- Prevention , Antibacterial agents -- Therapeutic use
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/13889 , vital:27354
- Description: Breast cancer is the most frequently diagnosed cancer in women worldwide.A treatment regime, both effective and safe and can only be achieved once more effective chemotherapeutic agents are discovered or identified. These “drugs” must selectively induce cell death such as apoptosis or necroptosis in the cancer cells. Apoptotic cell death allows a cell to “commit suicide” in genetically- controlled or programmed mechanism(s). The microenvironment of the tumour is important since a nurturing malignant environment is required for tumour maintenance, progression and ultimately the development of metastasis. Due to the correlation of the tumour microenvironment to aggressive tumour progression, emphasis should be placed on the constituents of the tumour’s microenvironment. In recent years, the understanding of intracellular pathways in cancer cells has increased rapidly, contributing to the development of drugs with more specific targets such as growth factors, signalling molecules, cell adhesion proteins, proteases, cell-cycle proteins, modulators of apoptosis and molecules that promote angiogenesis and metastasis. The main aim of this study was thus to identify a few potential or active compounds from a library of synthetically-derived compounds as possible alternative breast cancer treatment candidates.
- Full Text:
- Date Issued: 2017
The effects of terpenoids on the expression and function of cytokines and adipokines in pre-adipocytes and differentiated adipocytes
- Authors: Bloom, Carri-Ann
- Date: 2017
- Subjects: Terpenes , Cytokines , Fat cells
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/9208 , vital:26479
- Description: CURRENTLY UNDER EMBARGO UNTIL THE 26/4/2019: Type 2 diabetes is a metabolic disorder characterised by inflammation, insulin resistance and the inability of pancreatic β-cells to secrete enough insulin to produce a physiological effect. Obesity and high levels of triacylglycerol’s are associated with the development of Type 2 diabetes. Adipose tissue is an active endocrine organ that secretes various protein and peptide hormones, known as adipokines, which mediate important metabolic functions. In an insulin resistant and hyperglycaemic state, levels of anti-inflammatory adipokines, adiponectin, are reduced, whereas levels of pro-inflammatory cytokines, interleukin-6 and interleukin-1β, are elevated; this results in a shift from an anti- to a pro-inflammatory state that is accompanied by dysfunction and apoptosis of the pancreatic β-cells. Cannabis sativa L. has been traditionally used as an anti-inflammatory agent in Southern Africa, specifically treating snakebites, fever and malaria. Δ9-tetrahydrocannabinol is the main psychoactive compound derived from C. sativa, whereas the other major cannabinoids, cannabinol and cannabidiol, have shown anti-inflammatory and sedative properties respectively. Marrubiin is a compound derived from the plant Leonotis leonurus L. and has been traditionally used as an anti-inflammatory and anti-diabetic agent. To determine the effects of these compounds in a hyperglycaemic state, pre- and differentiated mouse adipocytes (3T3-L1 cells) were exposed for seven and fourteen days to the following treatments: Δ9-tetrahydrocannabinol, cannabidiol, cannabinol, marrubiin, anandamide (an endogenous endocannabinoid) and cannabis extract, individually and in combination, under normal glucose and hyperglycaemic conditions. Levels of adiponectin, interleukin-6, leptin, tumour-necrosis factor-α and interleukin-1β were quantified using mouse enzyme-linked immunosorbent assay kits and Oil Red O staining was carried out to determine lipid distribution and lipid droplet characteristics. Results indicate that various cannabinoids, in combination, mediate an anti-inflammatory effect by decreasing the expression of various pro-inflammatory cytokines, which may have allowed for a shift from a pro- to an anti-inflammatory state by these compounds, and may also contribute to the reduction of lipid, which may be used as a supplementary option to current diabetic treatment regimes.
- Full Text: false
- Date Issued: 2017
- Authors: Bloom, Carri-Ann
- Date: 2017
- Subjects: Terpenes , Cytokines , Fat cells
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/9208 , vital:26479
- Description: CURRENTLY UNDER EMBARGO UNTIL THE 26/4/2019: Type 2 diabetes is a metabolic disorder characterised by inflammation, insulin resistance and the inability of pancreatic β-cells to secrete enough insulin to produce a physiological effect. Obesity and high levels of triacylglycerol’s are associated with the development of Type 2 diabetes. Adipose tissue is an active endocrine organ that secretes various protein and peptide hormones, known as adipokines, which mediate important metabolic functions. In an insulin resistant and hyperglycaemic state, levels of anti-inflammatory adipokines, adiponectin, are reduced, whereas levels of pro-inflammatory cytokines, interleukin-6 and interleukin-1β, are elevated; this results in a shift from an anti- to a pro-inflammatory state that is accompanied by dysfunction and apoptosis of the pancreatic β-cells. Cannabis sativa L. has been traditionally used as an anti-inflammatory agent in Southern Africa, specifically treating snakebites, fever and malaria. Δ9-tetrahydrocannabinol is the main psychoactive compound derived from C. sativa, whereas the other major cannabinoids, cannabinol and cannabidiol, have shown anti-inflammatory and sedative properties respectively. Marrubiin is a compound derived from the plant Leonotis leonurus L. and has been traditionally used as an anti-inflammatory and anti-diabetic agent. To determine the effects of these compounds in a hyperglycaemic state, pre- and differentiated mouse adipocytes (3T3-L1 cells) were exposed for seven and fourteen days to the following treatments: Δ9-tetrahydrocannabinol, cannabidiol, cannabinol, marrubiin, anandamide (an endogenous endocannabinoid) and cannabis extract, individually and in combination, under normal glucose and hyperglycaemic conditions. Levels of adiponectin, interleukin-6, leptin, tumour-necrosis factor-α and interleukin-1β were quantified using mouse enzyme-linked immunosorbent assay kits and Oil Red O staining was carried out to determine lipid distribution and lipid droplet characteristics. Results indicate that various cannabinoids, in combination, mediate an anti-inflammatory effect by decreasing the expression of various pro-inflammatory cytokines, which may have allowed for a shift from a pro- to an anti-inflammatory state by these compounds, and may also contribute to the reduction of lipid, which may be used as a supplementary option to current diabetic treatment regimes.
- Full Text: false
- Date Issued: 2017
The Grootfontein aquifer at Mahikeng, South Africa as hydro-social system
- Authors: Cobbing, Jude Edmund
- Date: 2017
- Subjects: Groundwater -- South Africa -- Mahikeng Hydrogeology -- South Africa -- Mahikeng
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/21351 , vital:29484
- Description: The Grootfontein aquifer is located about 20 km south east of Mahikeng, North West Province, South Africa, and currently supplies about 20% of Mahikeng’s water. Formed in weathered Malmani Subgroup dolomites, the aquifer contains good quality groundwater that could potentially supply more of Mahikeng’s water, as well as provide a strategic reserve of water for use during droughts. Over-abstraction of groundwater from the aquifer, mainly by irrigating farmers but also by the boreholes supplying Mahikeng, has caused the natural groundwater level to drop at a rate of about 0.4 m per year since the 1970s, leading to water level declines of as much as 28 m in parts of the aquifer. Although the Grootfontein aquifer is one of the best studied aquifers in South Africa hydrogeologically, efforts to address these declines since the 1970s have largely failed. This research combines hydrogeological evidence with social research (interviews and participant-observation) and the principles of Earth Stewardship Science to argue that the aquifer functions as a hydro-social system, and that institutional characteristics are the root cause of a collective inability to restore the aquifer to its full potential as a water resource. A sub-optimal and undesirable Nash equilibrium prevails, in which major groundwater users are unable or unwilling to reduce abstraction. The situation has significant cost and risk implications for the environmental, economic and social sectors, and contributes to insecurity, pessimism, inequality and mistrust. An effective local forum with appropriate powers, supported and mandated by the Department of Water and Sanitation, is needed to begin the work of dismantling the sub-optimal equilibrium to realise the potential of the Grootfontein aquifer. Such a forum would require a shared understanding of the hydrogeological mechanisms of the aquifer as well as its social and institutional functioning, since these influence each other in complex ways.
- Full Text:
- Date Issued: 2017
- Authors: Cobbing, Jude Edmund
- Date: 2017
- Subjects: Groundwater -- South Africa -- Mahikeng Hydrogeology -- South Africa -- Mahikeng
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/21351 , vital:29484
- Description: The Grootfontein aquifer is located about 20 km south east of Mahikeng, North West Province, South Africa, and currently supplies about 20% of Mahikeng’s water. Formed in weathered Malmani Subgroup dolomites, the aquifer contains good quality groundwater that could potentially supply more of Mahikeng’s water, as well as provide a strategic reserve of water for use during droughts. Over-abstraction of groundwater from the aquifer, mainly by irrigating farmers but also by the boreholes supplying Mahikeng, has caused the natural groundwater level to drop at a rate of about 0.4 m per year since the 1970s, leading to water level declines of as much as 28 m in parts of the aquifer. Although the Grootfontein aquifer is one of the best studied aquifers in South Africa hydrogeologically, efforts to address these declines since the 1970s have largely failed. This research combines hydrogeological evidence with social research (interviews and participant-observation) and the principles of Earth Stewardship Science to argue that the aquifer functions as a hydro-social system, and that institutional characteristics are the root cause of a collective inability to restore the aquifer to its full potential as a water resource. A sub-optimal and undesirable Nash equilibrium prevails, in which major groundwater users are unable or unwilling to reduce abstraction. The situation has significant cost and risk implications for the environmental, economic and social sectors, and contributes to insecurity, pessimism, inequality and mistrust. An effective local forum with appropriate powers, supported and mandated by the Department of Water and Sanitation, is needed to begin the work of dismantling the sub-optimal equilibrium to realise the potential of the Grootfontein aquifer. Such a forum would require a shared understanding of the hydrogeological mechanisms of the aquifer as well as its social and institutional functioning, since these influence each other in complex ways.
- Full Text:
- Date Issued: 2017
The growth and recovery of mangroves at three South African study sites
- Authors: Mbense, Sinegugu
- Date: 2017
- Subjects: Mangrove forests -- South Africa Mangrove ecology -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/11931 , vital:27008
- Description: Mangroves in South Africa are prone to anthropogenic pressures such as browsing and trampling by livestock and by natural disturbances such as drought and floods. These mangroves exist at one of the most southerly limits in the world providing a unique opportunity to study recovery and resilience to change. This study used long term data at three South African study sites located in the subtropical (St Lucia Estuary) and warm temperate regions (Nxaxo and Kobonqaba estuaries) to compare mangrove growth rate, population structure and responses to disturbance. The first objective was investigated at St Lucia Estuary where site specific or microhabitat differences were measured to assess the influence of these on mangrove growth and population structure. It was suggested that site - specific variability would ensure mangrove survival and analysis showed that seedlings were present at different sites in different years. There was always some recruitment but often little survival to the next size class. Over time seedling numbers were quite variable and self – thinning of adults was evident. The second objective was to identify the environmental factors influencing population density and growth. Results showed that sediment moisture and salinity influenced seedling and adult density due to fluctuations in estuary water level. Mangrove growth rates for Avicennia marina in terms of height was faster (40 – 75 cm yr-1 ) at Site 1 where conditions were waterlogged and moderately saline and slower (5 – 25 cm yr1 ) in dry and hypersaline conditions at Site 4. Overall mangroves at St Lucia have shown persistence through drought and fluctuations in environmental conditions however resilience may be hindered at sites that are subjected to partially flooding and prolonged waterlogging. The second site was Nxaxo Estuary in the Eastern Cape where cattle exclusion plots (nonbrowsed) and control plots (browsed) were used to assess the recovery of A. marina trees from cattle browsing. Trees in the browsed plots showed no vertical growth while trees in the non-browsed plots grew significantly faster (5.4 ± 0.5 cm yr-1). When cattle were prevented from entering the mangrove area, the trees recovered fairly quickly and within 3 years growth was similar in both the non – browsed (17.9 ± 3.2 cm yr -1) and browsed plots (18 ± 1.6 cm yr -1). Lastly, mangrove recovery was investigated at Kobonqaba Estuary where long-term closure of the mouth to the sea resulted in high water levels, inundation of pneumatophores and die-back of the majority of the mangroves. This study measured the recovery of the mangroves by assessing changes in vegetation cover and sediment characteristics along transects. High initial porewater nutrient concentrations promoted salt marsh growth and plants increased average cover from 0% in 2011 to 18.9% (2013) and 50% in 2015. The total number of A. marina individuals increased from only seven to 27 individuals over four years. Salt marsh competition and facilitation will likely influence mangrove recovery in the future. Overall it was concluded that when a short term pressure (cattle browsing) is alleviated, mangrove forests even at warm temperate sites are able to recovery rapidly by increasing growth and seedling establishment. However, mangroves in the subtropical sites show more resilience and recovery potential to long term pressures such as fluctuating environmental conditions because of faster growth rates.
- Full Text:
- Date Issued: 2017
- Authors: Mbense, Sinegugu
- Date: 2017
- Subjects: Mangrove forests -- South Africa Mangrove ecology -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/11931 , vital:27008
- Description: Mangroves in South Africa are prone to anthropogenic pressures such as browsing and trampling by livestock and by natural disturbances such as drought and floods. These mangroves exist at one of the most southerly limits in the world providing a unique opportunity to study recovery and resilience to change. This study used long term data at three South African study sites located in the subtropical (St Lucia Estuary) and warm temperate regions (Nxaxo and Kobonqaba estuaries) to compare mangrove growth rate, population structure and responses to disturbance. The first objective was investigated at St Lucia Estuary where site specific or microhabitat differences were measured to assess the influence of these on mangrove growth and population structure. It was suggested that site - specific variability would ensure mangrove survival and analysis showed that seedlings were present at different sites in different years. There was always some recruitment but often little survival to the next size class. Over time seedling numbers were quite variable and self – thinning of adults was evident. The second objective was to identify the environmental factors influencing population density and growth. Results showed that sediment moisture and salinity influenced seedling and adult density due to fluctuations in estuary water level. Mangrove growth rates for Avicennia marina in terms of height was faster (40 – 75 cm yr-1 ) at Site 1 where conditions were waterlogged and moderately saline and slower (5 – 25 cm yr1 ) in dry and hypersaline conditions at Site 4. Overall mangroves at St Lucia have shown persistence through drought and fluctuations in environmental conditions however resilience may be hindered at sites that are subjected to partially flooding and prolonged waterlogging. The second site was Nxaxo Estuary in the Eastern Cape where cattle exclusion plots (nonbrowsed) and control plots (browsed) were used to assess the recovery of A. marina trees from cattle browsing. Trees in the browsed plots showed no vertical growth while trees in the non-browsed plots grew significantly faster (5.4 ± 0.5 cm yr-1). When cattle were prevented from entering the mangrove area, the trees recovered fairly quickly and within 3 years growth was similar in both the non – browsed (17.9 ± 3.2 cm yr -1) and browsed plots (18 ± 1.6 cm yr -1). Lastly, mangrove recovery was investigated at Kobonqaba Estuary where long-term closure of the mouth to the sea resulted in high water levels, inundation of pneumatophores and die-back of the majority of the mangroves. This study measured the recovery of the mangroves by assessing changes in vegetation cover and sediment characteristics along transects. High initial porewater nutrient concentrations promoted salt marsh growth and plants increased average cover from 0% in 2011 to 18.9% (2013) and 50% in 2015. The total number of A. marina individuals increased from only seven to 27 individuals over four years. Salt marsh competition and facilitation will likely influence mangrove recovery in the future. Overall it was concluded that when a short term pressure (cattle browsing) is alleviated, mangrove forests even at warm temperate sites are able to recovery rapidly by increasing growth and seedling establishment. However, mangroves in the subtropical sites show more resilience and recovery potential to long term pressures such as fluctuating environmental conditions because of faster growth rates.
- Full Text:
- Date Issued: 2017
The investigation of chemical variation in the stems and rhizomes of cissampelos capensis l. f. (menispermaceae) the Eastern Cape medicinal plant
- Authors: Latolla, Nehemiah Solomon
- Date: 2017
- Subjects: Plants -- Composition Medicinal plants Endemic plants
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/13970 , vital:27362
- Description: Cissampelos capensis L. f. (Menispermaceae) commonly known as “Mayisake” (Xhosa) and “Dawidjieswortel” (Afrikaans) is the most commonly used medicinal plant of the Menispermaceae family in South Africa. The rhizomes of Cissampelos capensis are the most used part of the plant to treat illnesses. This poses a threat to the ongoing conservation of this valuable endemic species. Thus, we studied the chemical variation and subsequently the bioactivity in the stems and rhizomes of Cissampelos capensis, the Eastern Cape medicinal plant, to suggest the possible use of the stems for medicinal purposes. We studied the variation in the chemical composition in the stems and the rhizomes by employing four different extraction methods; the methanolic-, non-polar-, alkaloidal- and Total Tertiary Alkaloidal (TTA) to extract compounds from Cissampelos capensis. Employing various chromatographic techniques, HPLC, NMR and LC/MS to investigate the chemical variation and the in vitro assays for the crude materials of the stems and rhizomes of Cissampelos capensis. We successfully documented a library of the phytochemicals content in Cissampelos capensis from three different regions in the Eastern Cape. We could profile different extraction methods, with the TTA extraction delivering the best comparative profile. Employing LC/MS and HPLC we identified eleven known alkaloidal compounds in the stems and rhizomes. We also isolated a known alkaloid, pronuciferine, from the TTA extract and a crystal structure of proto-quericitol from the methanolic extract, which was isolated for the first time from Cissampelos capensis. Preliminary in vitro results suggested anti-inflammatory activity in the methanolic extracts of the stems and rhizomes, while the TTA extracts showed some cytotoxicity. Finally, through analytical HPLC analysis this study found as high as 31% similarity between the chemical variation of the stems and rhizomes, but key alkaloids were not always present, indicating more work is needed before the stems can be recommended as a replacement for the rhizomes.
- Full Text:
- Date Issued: 2017
- Authors: Latolla, Nehemiah Solomon
- Date: 2017
- Subjects: Plants -- Composition Medicinal plants Endemic plants
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/13970 , vital:27362
- Description: Cissampelos capensis L. f. (Menispermaceae) commonly known as “Mayisake” (Xhosa) and “Dawidjieswortel” (Afrikaans) is the most commonly used medicinal plant of the Menispermaceae family in South Africa. The rhizomes of Cissampelos capensis are the most used part of the plant to treat illnesses. This poses a threat to the ongoing conservation of this valuable endemic species. Thus, we studied the chemical variation and subsequently the bioactivity in the stems and rhizomes of Cissampelos capensis, the Eastern Cape medicinal plant, to suggest the possible use of the stems for medicinal purposes. We studied the variation in the chemical composition in the stems and the rhizomes by employing four different extraction methods; the methanolic-, non-polar-, alkaloidal- and Total Tertiary Alkaloidal (TTA) to extract compounds from Cissampelos capensis. Employing various chromatographic techniques, HPLC, NMR and LC/MS to investigate the chemical variation and the in vitro assays for the crude materials of the stems and rhizomes of Cissampelos capensis. We successfully documented a library of the phytochemicals content in Cissampelos capensis from three different regions in the Eastern Cape. We could profile different extraction methods, with the TTA extraction delivering the best comparative profile. Employing LC/MS and HPLC we identified eleven known alkaloidal compounds in the stems and rhizomes. We also isolated a known alkaloid, pronuciferine, from the TTA extract and a crystal structure of proto-quericitol from the methanolic extract, which was isolated for the first time from Cissampelos capensis. Preliminary in vitro results suggested anti-inflammatory activity in the methanolic extracts of the stems and rhizomes, while the TTA extracts showed some cytotoxicity. Finally, through analytical HPLC analysis this study found as high as 31% similarity between the chemical variation of the stems and rhizomes, but key alkaloids were not always present, indicating more work is needed before the stems can be recommended as a replacement for the rhizomes.
- Full Text:
- Date Issued: 2017
The suitability of remote sensing for prioritising management of invasive plants in the Garden Route South Africa
- Gerolemou, Rosie Victoria, Roux, Dirk
- Authors: Gerolemou, Rosie Victoria , Roux, Dirk
- Date: 2017
- Subjects: Invasive plants -- Remote sensing , Invasive plants -- South Africa Image processing -- Digital techniques Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/14300 , vital:27538
- Description: Invasive tree species pose a huge problem in the Garden Route and are particularly damaging to aquatic ecosystems, including wetlands, riparian zones, lakes and estuaries. Therefore, this study aimed to determine priority areas for invasive tree species management, with a focus on aquatic ecosystems. This was achieved by using existing literature to identify priority species, based on their impact on aquatic ecosystems and their associated ecosystem services, and then testing the suitability of SPOT-6 and WorldView-3 multispectral data at detecting these focal species. The priority species identified were: Acacia cyclops (rooikrans), Acacia longifolia (long-leaved wattle), Acacia mearnsii (black wattle), Acacia melanoxylon (blackwood), Acacia saligna (Port Jackson willow), Eucalyptus camaldulensis (red river gum), Pinus pinaster (cluster pine) and Pinus radiata (radiata pine). The Random Forest classifier on SPOT-6 data achieved an overall accuracy of 62.5% and this method was consequently deemed ineffective at separating invasive tree species from other tree species in the Garden Route. The overall accuracy of the WorldView-3 classifier was higher (78.9%) but the cost of the data limited the use of more images for the detection of the focal species throughout the Garden Route. Therefore, to identify priority areas for invasive tree management, criteria derived from existing literature were input into spatial conservation planning software. The analysis identified the: Saasveld section of the Garden Route National Park, the Wilderness Lakes, Knysna Forest, Knysna Estuary, Tsitsikamma Forest around Stormsriver and a disturbed area of fynbos southeast of Kareedouw as management priorities. Currently spatial conservation planning software proved to be cost-affordable and useful tool and is recommended for invasive tree management in the Garden Route.
- Full Text:
- Date Issued: 2017
- Authors: Gerolemou, Rosie Victoria , Roux, Dirk
- Date: 2017
- Subjects: Invasive plants -- Remote sensing , Invasive plants -- South Africa Image processing -- Digital techniques Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/14300 , vital:27538
- Description: Invasive tree species pose a huge problem in the Garden Route and are particularly damaging to aquatic ecosystems, including wetlands, riparian zones, lakes and estuaries. Therefore, this study aimed to determine priority areas for invasive tree species management, with a focus on aquatic ecosystems. This was achieved by using existing literature to identify priority species, based on their impact on aquatic ecosystems and their associated ecosystem services, and then testing the suitability of SPOT-6 and WorldView-3 multispectral data at detecting these focal species. The priority species identified were: Acacia cyclops (rooikrans), Acacia longifolia (long-leaved wattle), Acacia mearnsii (black wattle), Acacia melanoxylon (blackwood), Acacia saligna (Port Jackson willow), Eucalyptus camaldulensis (red river gum), Pinus pinaster (cluster pine) and Pinus radiata (radiata pine). The Random Forest classifier on SPOT-6 data achieved an overall accuracy of 62.5% and this method was consequently deemed ineffective at separating invasive tree species from other tree species in the Garden Route. The overall accuracy of the WorldView-3 classifier was higher (78.9%) but the cost of the data limited the use of more images for the detection of the focal species throughout the Garden Route. Therefore, to identify priority areas for invasive tree management, criteria derived from existing literature were input into spatial conservation planning software. The analysis identified the: Saasveld section of the Garden Route National Park, the Wilderness Lakes, Knysna Forest, Knysna Estuary, Tsitsikamma Forest around Stormsriver and a disturbed area of fynbos southeast of Kareedouw as management priorities. Currently spatial conservation planning software proved to be cost-affordable and useful tool and is recommended for invasive tree management in the Garden Route.
- Full Text:
- Date Issued: 2017
The use of herbicides for the management of Eucalyptus coppice in South Africa
- Authors: Roberts, Jonathan Cecil
- Date: 2017
- Subjects: Eucalyptus grandis -- South Africa Herbicides -- South Africa
- Language: English
- Type: Thesis , Masters , Degree
- Identifier: http://hdl.handle.net/10948/20287 , vital:29205
- Description: The effectiveness and relatively low cost of herbicides has led to the near exclusion of non-herbicide methods for controlling weeds in commercial forestry plantations. However, any herbicide used within the forestry context has the potential to be toxic and/or alter ecosystem dynamics. In response to increased public concern, perceptions of risk, and compliance associated with forest certification standards and criterion, there is an increased need to provide alternative methods that can reduce reliance on herbicides. Even though adequate research has been implemented regarding herbicide use, little research has examined the implications of herbicide use or non-use throughout the full rotation. Since herbicide use is integrated within the management of eucalypt regeneration, it is critical that a comprehensive understanding of herbicide use be obtained before informed management decisions can be made. Only once this has been obtained, can reduced and judicious recourse to herbicide use be considered, both within the requirements of certification criteria and of good management practice (economic and site sustainability). The main objective of this thesis was to increase the understanding of herbicide use, as well the cost involved within the context of eucalypt coppice regimes in South Africa. Three field trials (two rotation-end, and one short-term) were implemented to achieve this objective, with herbicide use aimed at either killing eucalypt stumps if replanting, or control of secondary coppice regrowth if coppicing. The first trial was situated in Mpumalanga and evaluated which method of control would be best suited to reducing cost (cost-effective) and reliance on herbicides for killing eucalypt stumps and control of resulting coppice regrowth. Selected cut-stump and basal-frill treatments were included with triclopyr (480 g L-1 a.i.) applied to the cambium of difficult-to-kill Eucalyptus macarthurii H. Deane & Maiden stumps that had previously been coppiced multiple times. The resulting coppice regrowth was either manually removed, or glyphosate (360 g L-1 a.i.) applied to foliage. These treatments were integrated with non-chemical control methods, where E. dunnii Maiden seedlings were planted either between each stump row or within the row, to determine whether such treatments could further reduce the level of coppicing through shading. At rotation end, the different treatments tested had no significant influence on any of the E. dunnii growth variates. As there were no significant differences, the treatment with the lowest overall cost and herbicide used would be preferred. The application of triclopyr to the cut-surface following felling was the most cost-effective treatment. The differences in cost obtained is directly related to required follow-up coppice regrowth control operations and quantity of total herbicide applied (both triclopyr and glyphosate). It was hoped that the non-chemical control method (planting position of seedlings) would reduce the level of coppicing, however, within this trial, this did not occur. The second trial was situated in Zululand on Eucalyptus grandis x E. urophylla coppice that investigated different methods to control secondary coppice regrowth through either manual removal with a bush-knife, or the application of glyphosate (360 g L-1 a.i.) to the foliage. A range of herbicide rates (0.6%, 1.2% and 1.8%) was applied to the foliage of the secondary coppice regrowth when it reached a predetermined mean height (0.5 m, 1.0 m and 1.5 m). The objective was to determine the optimum rate and timing of control and to avoid glyphosate from being over-applied when managing this regrowth. No significant differences were detected between the different treatments for any of the growth variates at rotation end. The use of glyphosate, irrespective of rate and/or timing of application (as assessed by secondary coppice regrowth height) proved to be more cost-effective compared to manual removal of secondary coppice regrowth. Treatment efficacy in terms of treating secondary coppice regrowth increased with an increase in the rate of glyphosate applied (0% < 0.6% < 1.2% < 1 .8%), especially when treated at either 1.0 or 1.5 m in height. Although the volume of the glyphosate used increased with increasing secondary coppice regrowth height (0.5 m < 1.0 m < 1.5 m) due to the larger foliar spraying area, there was little difference in total glyphosate used when comparing the same herbicide rate across the three different heights. The most cost-effective treatment was that where glyphosate was applied at 1.2% when the secondary coppice regrowth was 1-1.5 m. The third trial (also located in Zululand on Eucalyptus grandis x E. urophylla) was implemented to test the knowledge gained in trial two, thereby determinng coppice management regimes that would facilitate mechanised harvesting. In this trial, coppice shoots were reduced to one stem per stump in one thinning operation (coppice reduction heights of 3.5 m, 4.5 m and 6.5 m), with the impact of increased secondary coppice regrowth monitored together with the testing of different control methods. An additional control treatment was included (current best operating practice) with coppice shoots thinned to two stems per stump at shoot height of 3.5 m, and thereafter to original stocking at stem height of 6.5 m. Herbicide rate and timing of application was based on the results obtained in the second trial, with glyphosate applied at 1.2% when the secondary coppice regrowth reached a mean height of approximately 1 m. At the final measurement date, the diameter at breast height for all three coppice reduction height treatments (3.5 m, 4.5 m and 6.5 m) were significantly larger than the additional control treatment. This can be attributed to the allocation of resources to the remaining stem at an earlier age, resulting in a growth benefit. For stocking, the 6.5 m coppice reduction height was significantly higher compared to both the 3.5 m and 4.5 m coppice reduction treatments, while not significantly different from the additional control. In this trial, secondary coppice regrowth had no effect on tree growth. Due to the short duration of this trial, a longer trial period would be necessary to obtain a full understanding of the impacts of the various coppice reduction treatments, and the resulting secondary coppice regrowth influence on selected coppice growth if left untreated. As several previous studies have shown the importance of controlling secondary coppice regrowth, it is recommended not to view the results of this present trial in isolation. On the basis of the results of this research, it can be concluded that the control of coppice regrowth with herbicides is more effective than any of the manual removal treatments in terms of cost, with manual control requiring more follow-up control operations. Even though the manual removal of coppice regrowth had no influence on growth of the remaining stems or planted trees, the potential injury to labourers or growing stock is still of concern. Therefore, the use of herbicides for controlling coppice regrowth would be preferable. However, if reduced herbicide-use is a major criterion, then coppice regrowth can be controlled manually, although at a higher cost.
- Full Text:
- Date Issued: 2017
- Authors: Roberts, Jonathan Cecil
- Date: 2017
- Subjects: Eucalyptus grandis -- South Africa Herbicides -- South Africa
- Language: English
- Type: Thesis , Masters , Degree
- Identifier: http://hdl.handle.net/10948/20287 , vital:29205
- Description: The effectiveness and relatively low cost of herbicides has led to the near exclusion of non-herbicide methods for controlling weeds in commercial forestry plantations. However, any herbicide used within the forestry context has the potential to be toxic and/or alter ecosystem dynamics. In response to increased public concern, perceptions of risk, and compliance associated with forest certification standards and criterion, there is an increased need to provide alternative methods that can reduce reliance on herbicides. Even though adequate research has been implemented regarding herbicide use, little research has examined the implications of herbicide use or non-use throughout the full rotation. Since herbicide use is integrated within the management of eucalypt regeneration, it is critical that a comprehensive understanding of herbicide use be obtained before informed management decisions can be made. Only once this has been obtained, can reduced and judicious recourse to herbicide use be considered, both within the requirements of certification criteria and of good management practice (economic and site sustainability). The main objective of this thesis was to increase the understanding of herbicide use, as well the cost involved within the context of eucalypt coppice regimes in South Africa. Three field trials (two rotation-end, and one short-term) were implemented to achieve this objective, with herbicide use aimed at either killing eucalypt stumps if replanting, or control of secondary coppice regrowth if coppicing. The first trial was situated in Mpumalanga and evaluated which method of control would be best suited to reducing cost (cost-effective) and reliance on herbicides for killing eucalypt stumps and control of resulting coppice regrowth. Selected cut-stump and basal-frill treatments were included with triclopyr (480 g L-1 a.i.) applied to the cambium of difficult-to-kill Eucalyptus macarthurii H. Deane & Maiden stumps that had previously been coppiced multiple times. The resulting coppice regrowth was either manually removed, or glyphosate (360 g L-1 a.i.) applied to foliage. These treatments were integrated with non-chemical control methods, where E. dunnii Maiden seedlings were planted either between each stump row or within the row, to determine whether such treatments could further reduce the level of coppicing through shading. At rotation end, the different treatments tested had no significant influence on any of the E. dunnii growth variates. As there were no significant differences, the treatment with the lowest overall cost and herbicide used would be preferred. The application of triclopyr to the cut-surface following felling was the most cost-effective treatment. The differences in cost obtained is directly related to required follow-up coppice regrowth control operations and quantity of total herbicide applied (both triclopyr and glyphosate). It was hoped that the non-chemical control method (planting position of seedlings) would reduce the level of coppicing, however, within this trial, this did not occur. The second trial was situated in Zululand on Eucalyptus grandis x E. urophylla coppice that investigated different methods to control secondary coppice regrowth through either manual removal with a bush-knife, or the application of glyphosate (360 g L-1 a.i.) to the foliage. A range of herbicide rates (0.6%, 1.2% and 1.8%) was applied to the foliage of the secondary coppice regrowth when it reached a predetermined mean height (0.5 m, 1.0 m and 1.5 m). The objective was to determine the optimum rate and timing of control and to avoid glyphosate from being over-applied when managing this regrowth. No significant differences were detected between the different treatments for any of the growth variates at rotation end. The use of glyphosate, irrespective of rate and/or timing of application (as assessed by secondary coppice regrowth height) proved to be more cost-effective compared to manual removal of secondary coppice regrowth. Treatment efficacy in terms of treating secondary coppice regrowth increased with an increase in the rate of glyphosate applied (0% < 0.6% < 1.2% < 1 .8%), especially when treated at either 1.0 or 1.5 m in height. Although the volume of the glyphosate used increased with increasing secondary coppice regrowth height (0.5 m < 1.0 m < 1.5 m) due to the larger foliar spraying area, there was little difference in total glyphosate used when comparing the same herbicide rate across the three different heights. The most cost-effective treatment was that where glyphosate was applied at 1.2% when the secondary coppice regrowth was 1-1.5 m. The third trial (also located in Zululand on Eucalyptus grandis x E. urophylla) was implemented to test the knowledge gained in trial two, thereby determinng coppice management regimes that would facilitate mechanised harvesting. In this trial, coppice shoots were reduced to one stem per stump in one thinning operation (coppice reduction heights of 3.5 m, 4.5 m and 6.5 m), with the impact of increased secondary coppice regrowth monitored together with the testing of different control methods. An additional control treatment was included (current best operating practice) with coppice shoots thinned to two stems per stump at shoot height of 3.5 m, and thereafter to original stocking at stem height of 6.5 m. Herbicide rate and timing of application was based on the results obtained in the second trial, with glyphosate applied at 1.2% when the secondary coppice regrowth reached a mean height of approximately 1 m. At the final measurement date, the diameter at breast height for all three coppice reduction height treatments (3.5 m, 4.5 m and 6.5 m) were significantly larger than the additional control treatment. This can be attributed to the allocation of resources to the remaining stem at an earlier age, resulting in a growth benefit. For stocking, the 6.5 m coppice reduction height was significantly higher compared to both the 3.5 m and 4.5 m coppice reduction treatments, while not significantly different from the additional control. In this trial, secondary coppice regrowth had no effect on tree growth. Due to the short duration of this trial, a longer trial period would be necessary to obtain a full understanding of the impacts of the various coppice reduction treatments, and the resulting secondary coppice regrowth influence on selected coppice growth if left untreated. As several previous studies have shown the importance of controlling secondary coppice regrowth, it is recommended not to view the results of this present trial in isolation. On the basis of the results of this research, it can be concluded that the control of coppice regrowth with herbicides is more effective than any of the manual removal treatments in terms of cost, with manual control requiring more follow-up control operations. Even though the manual removal of coppice regrowth had no influence on growth of the remaining stems or planted trees, the potential injury to labourers or growing stock is still of concern. Therefore, the use of herbicides for controlling coppice regrowth would be preferable. However, if reduced herbicide-use is a major criterion, then coppice regrowth can be controlled manually, although at a higher cost.
- Full Text:
- Date Issued: 2017
Tree toppling by elephants and its consequences in thicket mosaic vegetation of Addo Elephant National Park
- Authors: Mgqatsa, Nokubonga
- Date: 2017
- Subjects: Elephants -- Behavior -- South Africa -- Addo Elephant National Park Woody plants -- South Africa -- Addo Elephant National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/19365 , vital:28859
- Description: This study explored the extent of elephant tree toppling and possible cascading effects in Karoo Thicket Mosaic habitat in the Eastern Cape Province, South Africa. While the notion that elephants topple trees is well recognised, little is known about their indirect effects and the possible influence on several trophic levels. Changes brought about by elephants have the potential to influence microclimatic conditions, soil litter processes, plant community composition and other animals. Therefore, this study determined the impacts of elephants on tree toppling, and hence the production of coarse woody debris and the Coarse Woody Debris Profile. Additionally, I explored the consequences of elephant tree toppling on the plant community, small mammals and seed removal. Furthermore, I explored the potential factors facilitating the coexistence of woody plants and elephants. I compared coarse woody debris production and the Coarse Woody Debris Profile between sites with and without elephants. Further, I assessed the consequences of tree toppling in the elephant present site at a patch scale to explore the possible cascading effects of elephants. Firstly, I showed that elephants impacted woody plants through branch/stem breakages and toppling of trees, but that effects vary for different categories of the Coarse Woody Debris Profile. This result confirms the most recent findings that woody plants are at risk from elephant herbivory in Karoo Thicket Mosaic habitat. The elephant toppling effect on these landscapes is largely influenced by plant growth form, with woody trees suffering high levels of elephant toppling than shrubs of comparable size. However, toppled Pappea capensis is able to persist from being toppled by elephants, either through coppicing or resprouting. Additionally, I showed that toppled trees form discrete patches on the landscape, with altered microclimate and browsing pressures. While I detected no significant effect of these changes on plant composition and abundance within these patches, these findings indicate the possible influence of elephants on facilitating plant recruitment and altering plant communities of thicket through toppling of trees. Moreover, I showed that elephant toppling of trees provide habitat patches for small mammals, thus affecting seed removal by vertebrates within patches. These changes had no discernable effect on soil seed banks. However, they highlight the need to better understand the temporal dynamics of these patches and implications for seed dynamics and plant communities on the landscape. The results show the patterns of elephant impacts on woody plants and possible cascading effects in the presence of elephants. Therefore, the study advances our understanding of top-down effects of elephants and shows the relevance of understanding these effects in order to effectively manage elephant impacts in different systems.
- Full Text:
- Date Issued: 2017
- Authors: Mgqatsa, Nokubonga
- Date: 2017
- Subjects: Elephants -- Behavior -- South Africa -- Addo Elephant National Park Woody plants -- South Africa -- Addo Elephant National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/19365 , vital:28859
- Description: This study explored the extent of elephant tree toppling and possible cascading effects in Karoo Thicket Mosaic habitat in the Eastern Cape Province, South Africa. While the notion that elephants topple trees is well recognised, little is known about their indirect effects and the possible influence on several trophic levels. Changes brought about by elephants have the potential to influence microclimatic conditions, soil litter processes, plant community composition and other animals. Therefore, this study determined the impacts of elephants on tree toppling, and hence the production of coarse woody debris and the Coarse Woody Debris Profile. Additionally, I explored the consequences of elephant tree toppling on the plant community, small mammals and seed removal. Furthermore, I explored the potential factors facilitating the coexistence of woody plants and elephants. I compared coarse woody debris production and the Coarse Woody Debris Profile between sites with and without elephants. Further, I assessed the consequences of tree toppling in the elephant present site at a patch scale to explore the possible cascading effects of elephants. Firstly, I showed that elephants impacted woody plants through branch/stem breakages and toppling of trees, but that effects vary for different categories of the Coarse Woody Debris Profile. This result confirms the most recent findings that woody plants are at risk from elephant herbivory in Karoo Thicket Mosaic habitat. The elephant toppling effect on these landscapes is largely influenced by plant growth form, with woody trees suffering high levels of elephant toppling than shrubs of comparable size. However, toppled Pappea capensis is able to persist from being toppled by elephants, either through coppicing or resprouting. Additionally, I showed that toppled trees form discrete patches on the landscape, with altered microclimate and browsing pressures. While I detected no significant effect of these changes on plant composition and abundance within these patches, these findings indicate the possible influence of elephants on facilitating plant recruitment and altering plant communities of thicket through toppling of trees. Moreover, I showed that elephant toppling of trees provide habitat patches for small mammals, thus affecting seed removal by vertebrates within patches. These changes had no discernable effect on soil seed banks. However, they highlight the need to better understand the temporal dynamics of these patches and implications for seed dynamics and plant communities on the landscape. The results show the patterns of elephant impacts on woody plants and possible cascading effects in the presence of elephants. Therefore, the study advances our understanding of top-down effects of elephants and shows the relevance of understanding these effects in order to effectively manage elephant impacts in different systems.
- Full Text:
- Date Issued: 2017
Tribocorrosion properties of friction stir welded and laser welded titanium alloy
- Authors: Davoren, Brandon Hilton
- Date: 2017
- Subjects: Chemistry, Technical -- Research Materials -- Mechanical properties , Aluminum alloys
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/33250 , vital:32605
- Description: Titanium alloy Ti6Al4V has extensive uses in aerospace, dentistry and the biomedical industry. When used in these applications there is often a need to weld two or more pieces of titanium alloy together. This can be done by either friction stir weld or laser weld methods. These welded regions are often exposed to corrosive environments in addition to factors such as induced additional mechanical wear. Thus to accurately report on the viability of the material in a specific application, the corrosion, wear and their synergistic effects need to be studied. Friction stir welding, which is a well-suited method for joining plates of Ti6Al4V, creates regions in the material that are affected differently. These regions can be described as the parent material, advancing side, retreating side and the weld zone. The tribological properties of the different friction stir weld regions were analysed in air using different loads, frequencies, experimental duration and surrounding environments. When the applied load was increased some of the weld regions showed an increase in the specific wear rate. For example, the weld zone region showed a decrease when compared to the parent material. In this tribology study the effect of the counter material was evaluated. E52100, Si3N4, SS 316 and alumina counter materials were used in the test procedure which was conducted in air on the weld regions. The parent material was found to have the highest average specific wear rates with the four counter materials when compared to the weld zone samples. The regions affected by the friction stir weld process all showed, on average, lower specific wear rates than the parent material. For the various tested samples, the coefficient of friction and material compatibility that was found to be the most stable, was the alumina ball. Owing to this as well as its chemical stability, alumina was determined to be the best material for further tribocorrosion studies. The friction stir welded samples, that were cut from a cross section of a friction stir weld plate, were analyzed in 3.5% NaCl and dilute Harrison’s solution respectively. The effect of wear on the electrochemical properties was studied under open circuit voltage (OCV) and fixed 0.2 V and 0.4 V applied potential conditions respectively. The effect of wear on the corrosion properties was studied using potentiodynamic polarization. From analyzing the friction stir weld regions in both a wear and wear-free environment, the synergistic properties, namely the effect of wear on corrosion and the effect of corrosion on wear, were able to be calculated. The first electrochemical study was performed under OCV conditions. In the presence of applied wear, the open circuit potential of the friction stir weld samples, in both 3.5% NaCl and dilute Harrison’s solution, was found to decrease from the initial stabilized value. Of interest was the rate at which the OCV recovered. It was found to follow a second order repassivation growth model which was explained in terms of an initial film growth stage, followed by a film thickening stage that results in a new OCV. The second synergized electrochemical-wear study was under fixed 0.2 V and 0.4 V applied potential conditions. In both solutions, 3.5% NaCl and dilute Harrison’s solution, a large increase in the current was observed during the applied wear experiment. The samples submerged in 3.5% NaCl were found to have higher average currents during the wear experiment than those in dilute Harrison’s solution. The rapid decrease in the current, after the applied wear ceased, was found to also follow the second order repassivation model. The electrochemical-wear synergism was done by using potentiodynamic polarization tests. The friction stir weld regions as well as the laser samples were analysed in a wear as well as a wear-free environment in order to determine the effect that wear had on the corrosion properties. In both 3.5% NaCl and dilute Harrison’s solution the corrosion rates were found to increase by 100-fold when the wear was present. The effect of the wear process on corrosion could also be described by synergistic factor, where values close to 1 would imply that applied wear had little effect on the corrosion properties and vice versa. The synergistic factors showed that the corrosion rate was greatly affected by the presence of wear with corrosion synergistic factors of 20 and upward for the friction stir welded samples. The results showed that the weld zone region had a lower corrosion rate than the parent material. This implied that the main weld zone was shown to have the least effect of wear on corrosion and would therefore show the lowest likelihood of failure due to corrosion when compared to the parent material. The wear synergistic factor was found to be between 1 and 1.6 for the friction stir weld regions. This implied that the wear rates of the friction stir welded samples were slightly affected by the presence of a corrosive environment and that the wear properties of the laser welded samples were enhanced by the presence of a corrosive environment. Similar studies performed on laser welded samples showed unusually different results due to the small nature of the laser weld region, with inconclusive results when compared to the friction stir welded samples.
- Full Text:
- Date Issued: 2017
- Authors: Davoren, Brandon Hilton
- Date: 2017
- Subjects: Chemistry, Technical -- Research Materials -- Mechanical properties , Aluminum alloys
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/33250 , vital:32605
- Description: Titanium alloy Ti6Al4V has extensive uses in aerospace, dentistry and the biomedical industry. When used in these applications there is often a need to weld two or more pieces of titanium alloy together. This can be done by either friction stir weld or laser weld methods. These welded regions are often exposed to corrosive environments in addition to factors such as induced additional mechanical wear. Thus to accurately report on the viability of the material in a specific application, the corrosion, wear and their synergistic effects need to be studied. Friction stir welding, which is a well-suited method for joining plates of Ti6Al4V, creates regions in the material that are affected differently. These regions can be described as the parent material, advancing side, retreating side and the weld zone. The tribological properties of the different friction stir weld regions were analysed in air using different loads, frequencies, experimental duration and surrounding environments. When the applied load was increased some of the weld regions showed an increase in the specific wear rate. For example, the weld zone region showed a decrease when compared to the parent material. In this tribology study the effect of the counter material was evaluated. E52100, Si3N4, SS 316 and alumina counter materials were used in the test procedure which was conducted in air on the weld regions. The parent material was found to have the highest average specific wear rates with the four counter materials when compared to the weld zone samples. The regions affected by the friction stir weld process all showed, on average, lower specific wear rates than the parent material. For the various tested samples, the coefficient of friction and material compatibility that was found to be the most stable, was the alumina ball. Owing to this as well as its chemical stability, alumina was determined to be the best material for further tribocorrosion studies. The friction stir welded samples, that were cut from a cross section of a friction stir weld plate, were analyzed in 3.5% NaCl and dilute Harrison’s solution respectively. The effect of wear on the electrochemical properties was studied under open circuit voltage (OCV) and fixed 0.2 V and 0.4 V applied potential conditions respectively. The effect of wear on the corrosion properties was studied using potentiodynamic polarization. From analyzing the friction stir weld regions in both a wear and wear-free environment, the synergistic properties, namely the effect of wear on corrosion and the effect of corrosion on wear, were able to be calculated. The first electrochemical study was performed under OCV conditions. In the presence of applied wear, the open circuit potential of the friction stir weld samples, in both 3.5% NaCl and dilute Harrison’s solution, was found to decrease from the initial stabilized value. Of interest was the rate at which the OCV recovered. It was found to follow a second order repassivation growth model which was explained in terms of an initial film growth stage, followed by a film thickening stage that results in a new OCV. The second synergized electrochemical-wear study was under fixed 0.2 V and 0.4 V applied potential conditions. In both solutions, 3.5% NaCl and dilute Harrison’s solution, a large increase in the current was observed during the applied wear experiment. The samples submerged in 3.5% NaCl were found to have higher average currents during the wear experiment than those in dilute Harrison’s solution. The rapid decrease in the current, after the applied wear ceased, was found to also follow the second order repassivation model. The electrochemical-wear synergism was done by using potentiodynamic polarization tests. The friction stir weld regions as well as the laser samples were analysed in a wear as well as a wear-free environment in order to determine the effect that wear had on the corrosion properties. In both 3.5% NaCl and dilute Harrison’s solution the corrosion rates were found to increase by 100-fold when the wear was present. The effect of the wear process on corrosion could also be described by synergistic factor, where values close to 1 would imply that applied wear had little effect on the corrosion properties and vice versa. The synergistic factors showed that the corrosion rate was greatly affected by the presence of wear with corrosion synergistic factors of 20 and upward for the friction stir welded samples. The results showed that the weld zone region had a lower corrosion rate than the parent material. This implied that the main weld zone was shown to have the least effect of wear on corrosion and would therefore show the lowest likelihood of failure due to corrosion when compared to the parent material. The wear synergistic factor was found to be between 1 and 1.6 for the friction stir weld regions. This implied that the wear rates of the friction stir welded samples were slightly affected by the presence of a corrosive environment and that the wear properties of the laser welded samples were enhanced by the presence of a corrosive environment. Similar studies performed on laser welded samples showed unusually different results due to the small nature of the laser weld region, with inconclusive results when compared to the friction stir welded samples.
- Full Text:
- Date Issued: 2017