Shrub and bird community response to fire in dune thicket of the southeastern Cape, South Africa
- Authors: Strydom, Tiaan
- Date: 2020
- Subjects: Fire prevention -- Research -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47635 , vital:40260
- Description: Fire studies within the Cape Floristic Region (CFR) are restricted to the impacts of fire on plants and birds in fire-prone fynbos while little is known about post-fire responses of shrubs and birds in fire-avoiding subtropical dune thicket, which coexists with fynbos but burns on much longer cycles. Fire is deemed important for maintaining the boundaries between fynbos and thicket. It has been hypothesised that high-intensity fires prevent fire-dependent fynbos from being replaced by fireavoiding subtropical thicket (hereafter thicket) on dune landscapes of the CFR. I posit that (1) fire-related thicket shrub mortality would be size dependent, with smaller individuals suffering higher mortality than larger ones; and (2) that survival and resprouting vigour of thicket shrubs would be negatively correlated with fire intensity. In relation to the response of birds to fire I posit that (1) fire reduces bird species richness and bird abundance in thicket during the first two years post-fire; and (2) fire changes feeding guild composition and results in the loss of frugivorous birds. Extensive fires in dune thicket along the southeastern Cape coast presented the opportunity to assess the responses of thicket shrubs and birds to fire. For the thicket shrubs I assessed survival and resprouting vigour of thicket shrubs post-fire in relation to fire intensity and pre-fire shrub size at two dune landscapes (Cape St Francis and Knysna) in the CFR. I furthermore compared bird species richness, bird abundance and feeding guild composition between burnt and unburnt thicket (only at Knysna). A total of 29 species and 1112 individuals of thicket shrub were surveyed, with post-fire survival being high (83-85%). Smaller shrubs had a lower probability of post-fire survival than larger individuals but there was no consistent relationship between shrub mortality and fire intensity. Fire intensity had a positive effect on resprouting shoot count but a variable effect on resprouting volume. In the bird study a total of 66 bird species and 2404 individuals were recorded of which 52 species and 1176 individuals were in burnt thicket and 60 species and 1228 individuals were in unburnt thicket. Ten species occurred only in burnt thicket and 13 species only in unburnt thicket. Insectivores and generalists were the most common feeding guilds in terms of richness and abundance in both burnt and unburnt thicket. Frugivores were more abundant in unburnt thicket than burnt thicket, whereas granivores were more abundant in burnt thicket than unburnt thicket. I conclude that thicket shrubs and bird communities are resilient to fire. Prescribed high-intensity fires in dune landscapes are unlikely to reduce the extent of thicket in fynbos or radically change the bird communities. The effects of fire on thicket shrubs and birds are likely to be short-lived as thicket shrubs resprout vigorously after fire resulting in rapid recovery of vegetation and thus bird habitat structure. However, frequent fires may prevent the encroachment of thicket shrub juveniles into fynbos, owing to the greater vulnerability of small shrubs to fire. Most recruitment of thicket shrub individuals into fynbos is via ramets that likely originate from well-established plants in mature thicket stands. These mature unburnt thicket stands provide habitat for various forest bird species and can function as refuge areas for birds and other wildlife in fire-prone landscapes. However, there is no need for managers to take any precautions when implementing controlled burns or controlling wildfires because not all thicket patches in the landscape are likely to burn.
- Full Text:
- Date Issued: 2020
- Authors: Strydom, Tiaan
- Date: 2020
- Subjects: Fire prevention -- Research -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47635 , vital:40260
- Description: Fire studies within the Cape Floristic Region (CFR) are restricted to the impacts of fire on plants and birds in fire-prone fynbos while little is known about post-fire responses of shrubs and birds in fire-avoiding subtropical dune thicket, which coexists with fynbos but burns on much longer cycles. Fire is deemed important for maintaining the boundaries between fynbos and thicket. It has been hypothesised that high-intensity fires prevent fire-dependent fynbos from being replaced by fireavoiding subtropical thicket (hereafter thicket) on dune landscapes of the CFR. I posit that (1) fire-related thicket shrub mortality would be size dependent, with smaller individuals suffering higher mortality than larger ones; and (2) that survival and resprouting vigour of thicket shrubs would be negatively correlated with fire intensity. In relation to the response of birds to fire I posit that (1) fire reduces bird species richness and bird abundance in thicket during the first two years post-fire; and (2) fire changes feeding guild composition and results in the loss of frugivorous birds. Extensive fires in dune thicket along the southeastern Cape coast presented the opportunity to assess the responses of thicket shrubs and birds to fire. For the thicket shrubs I assessed survival and resprouting vigour of thicket shrubs post-fire in relation to fire intensity and pre-fire shrub size at two dune landscapes (Cape St Francis and Knysna) in the CFR. I furthermore compared bird species richness, bird abundance and feeding guild composition between burnt and unburnt thicket (only at Knysna). A total of 29 species and 1112 individuals of thicket shrub were surveyed, with post-fire survival being high (83-85%). Smaller shrubs had a lower probability of post-fire survival than larger individuals but there was no consistent relationship between shrub mortality and fire intensity. Fire intensity had a positive effect on resprouting shoot count but a variable effect on resprouting volume. In the bird study a total of 66 bird species and 2404 individuals were recorded of which 52 species and 1176 individuals were in burnt thicket and 60 species and 1228 individuals were in unburnt thicket. Ten species occurred only in burnt thicket and 13 species only in unburnt thicket. Insectivores and generalists were the most common feeding guilds in terms of richness and abundance in both burnt and unburnt thicket. Frugivores were more abundant in unburnt thicket than burnt thicket, whereas granivores were more abundant in burnt thicket than unburnt thicket. I conclude that thicket shrubs and bird communities are resilient to fire. Prescribed high-intensity fires in dune landscapes are unlikely to reduce the extent of thicket in fynbos or radically change the bird communities. The effects of fire on thicket shrubs and birds are likely to be short-lived as thicket shrubs resprout vigorously after fire resulting in rapid recovery of vegetation and thus bird habitat structure. However, frequent fires may prevent the encroachment of thicket shrub juveniles into fynbos, owing to the greater vulnerability of small shrubs to fire. Most recruitment of thicket shrub individuals into fynbos is via ramets that likely originate from well-established plants in mature thicket stands. These mature unburnt thicket stands provide habitat for various forest bird species and can function as refuge areas for birds and other wildlife in fire-prone landscapes. However, there is no need for managers to take any precautions when implementing controlled burns or controlling wildfires because not all thicket patches in the landscape are likely to burn.
- Full Text:
- Date Issued: 2020
Solid waste management practices in Joe Slovo township, Nelson Mandela Bay Municipality
- Mngomezulu, Sibongangani Khonelihle
- Authors: Mngomezulu, Sibongangani Khonelihle
- Date: 2020
- Subjects: Refuse and refuse disposal -- Management , Refuse and refuse disposal -- Environmental aspects Refuse and refuse disposal -- South Africa -- Port Elizabeth -- Management
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46185 , vital:39512
- Description: Solid waste management practice is one of the essential service deliveries that should exist in all places. The method of handling, storage and processing solid waste at household is key and it plays a significant role in public health, ensuring a safe environment and in the efficiency of municipal solid waste. Previous research has revealed that solid waste management is a global issue and the lack of awareness and involvement of communities is escalating the problem. In addition, studies also disclosed that solid waste produced by inhabitants is recyclable, therefore waste management practice must implement new systems that are sustainable, to improve waste management practices. Hence, addressing solid waste management challenges would have a positive impact on the goals of achieving a health-city concept which promotes sustainable development. The aim of this study was to examine solid waste management practices that hinder sustainable human settlements. The methodology used included an extensive literature review, field observation and a field study conducted in Joe Slovo West Township. A quantitative study approach that is based on a positivism paradigm and a random sampling technique was adopted. The descriptive method of data analysis was employed, and the findings and the interpretations are presented through tables, graphs and images. Analysis of the findings revealed that institutional, fiscal/economic, development, socio-economic and policy matters are the factors holding back existing solid waste management practices in Joe Slovo Township. Key recommendations include that the solid waste management system needs to be improved and that enhancing the ease of waste recycling as an economic activity and as a practice should be pursued and that residents should be educated and encouraged to separate their waste before disposal while an incentive should be provided for this to stimulate community participation.
- Full Text:
- Date Issued: 2020
- Authors: Mngomezulu, Sibongangani Khonelihle
- Date: 2020
- Subjects: Refuse and refuse disposal -- Management , Refuse and refuse disposal -- Environmental aspects Refuse and refuse disposal -- South Africa -- Port Elizabeth -- Management
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46185 , vital:39512
- Description: Solid waste management practice is one of the essential service deliveries that should exist in all places. The method of handling, storage and processing solid waste at household is key and it plays a significant role in public health, ensuring a safe environment and in the efficiency of municipal solid waste. Previous research has revealed that solid waste management is a global issue and the lack of awareness and involvement of communities is escalating the problem. In addition, studies also disclosed that solid waste produced by inhabitants is recyclable, therefore waste management practice must implement new systems that are sustainable, to improve waste management practices. Hence, addressing solid waste management challenges would have a positive impact on the goals of achieving a health-city concept which promotes sustainable development. The aim of this study was to examine solid waste management practices that hinder sustainable human settlements. The methodology used included an extensive literature review, field observation and a field study conducted in Joe Slovo West Township. A quantitative study approach that is based on a positivism paradigm and a random sampling technique was adopted. The descriptive method of data analysis was employed, and the findings and the interpretations are presented through tables, graphs and images. Analysis of the findings revealed that institutional, fiscal/economic, development, socio-economic and policy matters are the factors holding back existing solid waste management practices in Joe Slovo Township. Key recommendations include that the solid waste management system needs to be improved and that enhancing the ease of waste recycling as an economic activity and as a practice should be pursued and that residents should be educated and encouraged to separate their waste before disposal while an incentive should be provided for this to stimulate community participation.
- Full Text:
- Date Issued: 2020
Spatio-temporal variation of the land surface parameters in Temperature, in King Williams Town, Eastern Cape Province, South Africa
- Authors: Willie, Yanga Adrian
- Date: 2020
- Subjects: Environmental sciences
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/12106 , vital:39152
- Description: The world is currently experiencing unprecedented urban growth. The influx of people into urban areas from rural areas is motivated by both economic and social factors such as increased employment opportunities. The latter is a result of, in part, industrialization, and the perceived higher standard of living that is often associated with access to better infrastructure. Surface Heat Island (SHI) is a phenomenon whereby urban areas experience higher surface temperatures than the surrounding rural areas. The presence of the SHI in urban areas has a negative impact not only on city dwellers, but also on the environment and the economy. The development of SHI is often associated with patterns of land use and land cover in urban areas. Numerous methods exist that can be used to study SHI’s. Literature suggests that Land Surface Temperature (LST), derived from satellite imagery, is a proven method that produces reliable results. The aim of this study was to evaluate the SHI in King Williams Town by studying the relationship between land surface temperatures, land cover and land cover indices. The derived indices are the Normalized Difference Vegetation Index (NDVI) and Normalized Difference Built up Index (NDBI). These indices were selected because they are representative of the land cover scheme used in the research study. This study was conducted in the King Williams town area between the years 1995 and 2018 the land surface temperature was derived from Landsat ETM + high thermal band data. The findings from this study provide an idea on the correlation between satellite derived land surface temperature and the land modification which occurred during the urbanization of King Williams Town during a 23 year period between1995 and 2018. The built up land category was the most influential in the development of high land surface temperature levels , vegetation had an opposite effect as a series of data sets illustrated that vegetated areas had a iv cooling effect on the surface. Water bodies in the study area had an insignificant effect on the Surface temperature levels while the grass lands weren’t as cooling as the vegetation but provided a cooling environment in the study area .The spatial distribution of areas of high surface temperature (hot spots) was discovered to be concentrated in the urban areas of the study area which is in the northwest region of the study area and correlates to the land cover and land cover indices associated with built up and artificial surfaces. The cooler areas or patches of land with lower values of land surface temperature were distributed on the outskirts of the study area away from the CBD and residential areas. This was the case because of the high concentration of vegetation and thicker grass lands in those regions.
- Full Text:
- Date Issued: 2020
- Authors: Willie, Yanga Adrian
- Date: 2020
- Subjects: Environmental sciences
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/12106 , vital:39152
- Description: The world is currently experiencing unprecedented urban growth. The influx of people into urban areas from rural areas is motivated by both economic and social factors such as increased employment opportunities. The latter is a result of, in part, industrialization, and the perceived higher standard of living that is often associated with access to better infrastructure. Surface Heat Island (SHI) is a phenomenon whereby urban areas experience higher surface temperatures than the surrounding rural areas. The presence of the SHI in urban areas has a negative impact not only on city dwellers, but also on the environment and the economy. The development of SHI is often associated with patterns of land use and land cover in urban areas. Numerous methods exist that can be used to study SHI’s. Literature suggests that Land Surface Temperature (LST), derived from satellite imagery, is a proven method that produces reliable results. The aim of this study was to evaluate the SHI in King Williams Town by studying the relationship between land surface temperatures, land cover and land cover indices. The derived indices are the Normalized Difference Vegetation Index (NDVI) and Normalized Difference Built up Index (NDBI). These indices were selected because they are representative of the land cover scheme used in the research study. This study was conducted in the King Williams town area between the years 1995 and 2018 the land surface temperature was derived from Landsat ETM + high thermal band data. The findings from this study provide an idea on the correlation between satellite derived land surface temperature and the land modification which occurred during the urbanization of King Williams Town during a 23 year period between1995 and 2018. The built up land category was the most influential in the development of high land surface temperature levels , vegetation had an opposite effect as a series of data sets illustrated that vegetated areas had a iv cooling effect on the surface. Water bodies in the study area had an insignificant effect on the Surface temperature levels while the grass lands weren’t as cooling as the vegetation but provided a cooling environment in the study area .The spatial distribution of areas of high surface temperature (hot spots) was discovered to be concentrated in the urban areas of the study area which is in the northwest region of the study area and correlates to the land cover and land cover indices associated with built up and artificial surfaces. The cooler areas or patches of land with lower values of land surface temperature were distributed on the outskirts of the study area away from the CBD and residential areas. This was the case because of the high concentration of vegetation and thicker grass lands in those regions.
- Full Text:
- Date Issued: 2020
Structure and interaction studies of beta-amyloid in the search for new lead compounds for the treatment of Alzheimer’s disease
- Authors: Mtini, Onke
- Date: 2020
- Subjects: Alzheimer's disease -- Chemotherapy , Alzheimer's disease -- Treatment , Amyloid beta-protein , Oxidative stress , Protein binding , South African Natural Compounds Database
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167574 , vital:41493
- Description: Alzheimer’s disease (AD) is the most devastating neurodegenerative disorder that effects the aging population worldwide. In this study three hypotheses of AD are explored, the β-amyloid cascade hypothesis, the β-amyloid metal binding hypothesis and the oxidative stress hypothesis are explored. In the first case compounds from the South African Natural Compounds Database (SANCDB) are docked to models of β-amyloid fibrils and the properties of these fibrils under pulling simulations are compared to a known small molecule disruptor of β-amyloid, wgx-50. In these simulations SANCDB compounds are identified that disrupt β-amyloid in a similar manner to wgx-50. In these simulations the disruption to the free energy of binding of chains to the fibrils is quantified. For metal binding and oxidative stress hypotheses, problems in simulation arise due to only fragments of β-amyloid being present in the Research Collaboratory for Structural Bioinformatics protein data bank (RCSB PDB), as determined from NMR experiments. In this work, β-amyloid is set up under periodic boundary conditions to simulate a fibril under reasonable computational time. Within these periodic boundary conditions, β-amyloid has been solvated in copper and zinc rich environments and diffusion of these metals around the fibrils has been explored. The localization of these metals (in simulation only using van der Waal’s and electrostatic terms) around the fibril has led us to explore other possible metal binding sites. Metal bound to the infinite fibril has been optimized at the QM/MM level and some of the reactive oxygen species in the presence of the fibril are quantified.
- Full Text:
- Date Issued: 2020
- Authors: Mtini, Onke
- Date: 2020
- Subjects: Alzheimer's disease -- Chemotherapy , Alzheimer's disease -- Treatment , Amyloid beta-protein , Oxidative stress , Protein binding , South African Natural Compounds Database
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167574 , vital:41493
- Description: Alzheimer’s disease (AD) is the most devastating neurodegenerative disorder that effects the aging population worldwide. In this study three hypotheses of AD are explored, the β-amyloid cascade hypothesis, the β-amyloid metal binding hypothesis and the oxidative stress hypothesis are explored. In the first case compounds from the South African Natural Compounds Database (SANCDB) are docked to models of β-amyloid fibrils and the properties of these fibrils under pulling simulations are compared to a known small molecule disruptor of β-amyloid, wgx-50. In these simulations SANCDB compounds are identified that disrupt β-amyloid in a similar manner to wgx-50. In these simulations the disruption to the free energy of binding of chains to the fibrils is quantified. For metal binding and oxidative stress hypotheses, problems in simulation arise due to only fragments of β-amyloid being present in the Research Collaboratory for Structural Bioinformatics protein data bank (RCSB PDB), as determined from NMR experiments. In this work, β-amyloid is set up under periodic boundary conditions to simulate a fibril under reasonable computational time. Within these periodic boundary conditions, β-amyloid has been solvated in copper and zinc rich environments and diffusion of these metals around the fibrils has been explored. The localization of these metals (in simulation only using van der Waal’s and electrostatic terms) around the fibril has led us to explore other possible metal binding sites. Metal bound to the infinite fibril has been optimized at the QM/MM level and some of the reactive oxygen species in the presence of the fibril are quantified.
- Full Text:
- Date Issued: 2020
Symmetry and asymmetry in electrocatalysis: enhancing the electrocatalytic activity of phthalocyanines through synergy with doped graphene quantum dots
- Nkhahle, Reitumetse Precious
- Authors: Nkhahle, Reitumetse Precious
- Date: 2020
- Subjects: Phthalocyanines , Quantum dots , Graphene
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117585 , vital:34529
- Description: An exploration on the enhancement of the electrocatalytic activity of phthalocyanines (Pcs) through coupling with a series of graphene quantum dots (GQDs) is undertaken. The preliminary studies using symmetrical Pcs, a cobalt and an iron chloride tetra substituted diethylaminophenoxy Pc (complexes 1 and 2), for the electro-oxidation of nitrite revealed through the various sequential modifications that doped GQDs fare better than their pristine counterparts with respect to improving the electrocatalytic behaviour of Pcs, in particular, the nitrogen-doped GQDs (NGQDs). Following up on this, a series of asymmetric Pc complexes; 2,9,16-tris-(4-tert-butylphenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (3), 2,9,16-tris-(4-tert-butylphenoxy) mono aminophenoxy phthalocyanato cobalt (II) (4), 2,9,16-tris-(3-diethylamino)phenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (5) and 2,9,16-tris-(3-diethylamino)phenoxy) mono aminophenoxy phthalocyanato cobalt (II) (6) was prepared in which push-pull systems were compared to other asymmetric complexes that lack this effect towards the electrocatalytic sensing of hydrazine. All asymmetric complexes (3-6) were π-stacked to the NGQDs while those with an NH2 group (4 and 6), were also covalently linked to the NGQDs. These complexes and their corresponding conjugates were characterized accordingly and applied as electrocatalysts in the oxidation of hydrazine. The electrochemical studies revealed that π π stacking yields better responses (higher sensitivities and lower limits of detection) than covalent linking because there are less forces acting on the graphene network. Covalent linking introduces both tensile and compressive forces which in turn results in an increase in the ID/IG ratio and that is unfavourable for electrocatalysis. In comparing the electrodes composed of the π-stacked conjugates to those altered through sequential modifications, despite the conditions not being the same, it can be inferred that the magnitude of the electrostatic forces between the Pcs and the GQDs also plays a significant role in electrocatalysis. The π-stacked conjugates, owing to the manner in which they were prepared, have stronger electrostatic forces acting between the Pc and GQDs hence they were able to elicit a better electrochemical response than the sequentially modified electrodes. In addition to that, it appears that asymmetric Pcs are better electrocatalysts in comparison to the symmetric Pcs.
- Full Text:
- Date Issued: 2020
- Authors: Nkhahle, Reitumetse Precious
- Date: 2020
- Subjects: Phthalocyanines , Quantum dots , Graphene
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117585 , vital:34529
- Description: An exploration on the enhancement of the electrocatalytic activity of phthalocyanines (Pcs) through coupling with a series of graphene quantum dots (GQDs) is undertaken. The preliminary studies using symmetrical Pcs, a cobalt and an iron chloride tetra substituted diethylaminophenoxy Pc (complexes 1 and 2), for the electro-oxidation of nitrite revealed through the various sequential modifications that doped GQDs fare better than their pristine counterparts with respect to improving the electrocatalytic behaviour of Pcs, in particular, the nitrogen-doped GQDs (NGQDs). Following up on this, a series of asymmetric Pc complexes; 2,9,16-tris-(4-tert-butylphenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (3), 2,9,16-tris-(4-tert-butylphenoxy) mono aminophenoxy phthalocyanato cobalt (II) (4), 2,9,16-tris-(3-diethylamino)phenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (5) and 2,9,16-tris-(3-diethylamino)phenoxy) mono aminophenoxy phthalocyanato cobalt (II) (6) was prepared in which push-pull systems were compared to other asymmetric complexes that lack this effect towards the electrocatalytic sensing of hydrazine. All asymmetric complexes (3-6) were π-stacked to the NGQDs while those with an NH2 group (4 and 6), were also covalently linked to the NGQDs. These complexes and their corresponding conjugates were characterized accordingly and applied as electrocatalysts in the oxidation of hydrazine. The electrochemical studies revealed that π π stacking yields better responses (higher sensitivities and lower limits of detection) than covalent linking because there are less forces acting on the graphene network. Covalent linking introduces both tensile and compressive forces which in turn results in an increase in the ID/IG ratio and that is unfavourable for electrocatalysis. In comparing the electrodes composed of the π-stacked conjugates to those altered through sequential modifications, despite the conditions not being the same, it can be inferred that the magnitude of the electrostatic forces between the Pcs and the GQDs also plays a significant role in electrocatalysis. The π-stacked conjugates, owing to the manner in which they were prepared, have stronger electrostatic forces acting between the Pc and GQDs hence they were able to elicit a better electrochemical response than the sequentially modified electrodes. In addition to that, it appears that asymmetric Pcs are better electrocatalysts in comparison to the symmetric Pcs.
- Full Text:
- Date Issued: 2020
Synthesis and application of fluorescent triazolyl-coumarin based chemosensors
- Authors: Schoeman, Stiaan
- Date: 2020
- Subjects: Chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47454 , vital:39992
- Description: The search for a fluorescent chemosensor with high selectivity and sensitivity that can be used for the detection of trace amounts of a toxic transition metal or heavy metal ions have gained immense popularity in recent years. Coumarin derivatives have been widely used as the basis of these fluorescent chemosensors by which a 1,2,3-triazole ring is used as the binding site for such metal ions. The benefits of chemosensors include nearly eliminating the need for tedious sample preparation and highly skilled operators. Therefore, enabling quantitative and qualitative measurement in both a lab setting and on-site. In addition, chemosensors provide a more sensitive and selective detection method at low-cost. A variety of chemosensors were designed and synthesized, in which some synthesis steps were refined to obtain better yields and purer products. Chemosensors designed, in this study, can be divided into novel triazolyl-coumarin derivatives without a spacer 1C – 1D and with a spacer between the coumarin and triazole ring (2D and 2E). 1C – 1D were characterized by 1H NMR, 13C NMR and IR and photophysical properties were investigated in DMF. 2D and 2E could not be purified and further investigation was discontinued. An overall enhancement was observed for the chemosensors 1C – 1D in the presence of 24 different ions that were tested. 1C had a quenching effect in the presence of Cd2+, however, competition studies revealed that 1C is not selective in the presence of competing metal cations. Molecular modelling studies were performed on sensors 1C – 1G in the presence of various ions. The molecular modelling studies provided invaluable insights into the binding of the selected metal ions as well as revealed a variety of binding sites. In addition, the space-filled depictions offered insights into the overlapping during binding which had an effect in the electrostatic potential maps of the chemosensors..
- Full Text:
- Date Issued: 2020
- Authors: Schoeman, Stiaan
- Date: 2020
- Subjects: Chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47454 , vital:39992
- Description: The search for a fluorescent chemosensor with high selectivity and sensitivity that can be used for the detection of trace amounts of a toxic transition metal or heavy metal ions have gained immense popularity in recent years. Coumarin derivatives have been widely used as the basis of these fluorescent chemosensors by which a 1,2,3-triazole ring is used as the binding site for such metal ions. The benefits of chemosensors include nearly eliminating the need for tedious sample preparation and highly skilled operators. Therefore, enabling quantitative and qualitative measurement in both a lab setting and on-site. In addition, chemosensors provide a more sensitive and selective detection method at low-cost. A variety of chemosensors were designed and synthesized, in which some synthesis steps were refined to obtain better yields and purer products. Chemosensors designed, in this study, can be divided into novel triazolyl-coumarin derivatives without a spacer 1C – 1D and with a spacer between the coumarin and triazole ring (2D and 2E). 1C – 1D were characterized by 1H NMR, 13C NMR and IR and photophysical properties were investigated in DMF. 2D and 2E could not be purified and further investigation was discontinued. An overall enhancement was observed for the chemosensors 1C – 1D in the presence of 24 different ions that were tested. 1C had a quenching effect in the presence of Cd2+, however, competition studies revealed that 1C is not selective in the presence of competing metal cations. Molecular modelling studies were performed on sensors 1C – 1G in the presence of various ions. The molecular modelling studies provided invaluable insights into the binding of the selected metal ions as well as revealed a variety of binding sites. In addition, the space-filled depictions offered insights into the overlapping during binding which had an effect in the electrostatic potential maps of the chemosensors..
- Full Text:
- Date Issued: 2020
Synthesis and characterisation of lanthanide complexes with potential nitrogen- and oxygen-donor schiff base ligands
- Authors: Pikoli, Sibongile
- Date: 2020
- Subjects: Rare earths , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47050 , vital:39778
- Description: This research describes the coordination chemistry of lanthanide complexes with potentially multidentate nitrogen- and oxygen-donor Schiff base derivatives. The studies were performed using various physico-chemical techniques including melting point, IR and NMR spectroscopy, UV-Vis spectroscopy, elemental analyses, conductivity measurements, X-ray crystallography and cyclic voltammetry. The reaction of [Ln(NO3)3·xH2O] (Ln = Nd, Gd, Yb; x = 6 for Nd and Gd, x = 5 for Yb) with the flexible salen-type Schiff base ligand 1,3-bis(o-hydroxybenzylideneamino)propane (H2L1) produced three polynuclear complexes with the general formulae {[Nd(µH2L1)4(NO3)3]·2H2O}n and [Ln(µ-H2L1)2(NO3)6(H2L1)] (Ln = Gd and Yb). Single-crystal Xray crystallography revealed a ten-coordinate polymeric Nd(III) complex that crystallised in the monoclinic space group P21/c, and isostructural nine-coordinate binuclear Gd(III) and Yb(III) complexes (triclinic system, space group P-1). The lanthanide contraction effect is clear across the series. The flexible nature of HL2 results in the self-assembly of the Nd(III) complex in a 1D polymer chain by acting as the bridge between the metal ions. The Nd-Ophenolate bond distances are 2.403(18), 2.463(17), 2.379(17) and 2.367(19) Å and the average Nd-Onitrate bond length is 2.671 Å. Furthermore, the electronic absorption spectra displays 4f→4f transitions solely for the neodymium(III) compound. The syntheses and characterisation of the lanthanide complexes, [La(HL2)3(NO3)3], [Dy(HL2)2(NO3)3] and [Dy(HL2)2Cl3(H2O)]·2CH2Cl2 with the o-vanillin-derived Schiff base ligand 2-methoxy-6-[(E)-(phenylimino)methyl]phenol (HL2) are reported. The nitro-stabilised La(III) and Dy(III) compounds are ten-coordinate with metabidiminished icosahedron and sphenocorona geometries, respectively. Substitution of the nitrate with chloride ions in the starting metal compounds yielded an eight-coordinate Dy(III) complex that adopts the biaugmented trigonal prism geometry. For all three complexes, HL2 exists as a zwitterion that is bound to the metal centre in a mono- and bidentate fashion via the phenolate and methoxy oxygen atoms. The dysprosium(III) chloride complex is stabilised by both intramolecular N−H···O and intermolecular O−H···C1 hydrogen bonds, while the crystal packing of the Ln(III) nitrate complexes is ensured by mainly intramolecular N−H···O hydrogen bonds. Fluorescence studies displayed characteristic Dy(III) f→f transitions (4F9/2 → 6H15/2), which suggest the ligand HL2 is an effective organic antenna to absorb and transfer energy to the dysprosium ion. A series of mononuclear Nd(III) complexes with the Schiff base derivatives 2-methoxy-6-[(E)(phenylimino)methyl]phenol (HL2), 5-methoxy-2-[(E)-(phenylimino)methyl]phenol (HL3) and 2-methoxy-6-{(E)-[(2-methoxyphenyl)imino]methyl}phenol (HL4) yielded structurally diverse complexes defined by the formulae [Nd(HL2)2(NO3)3], [Nd(HL3)3(NO3)3] and [Nd(HL4)2(NO3)3]·CH3OH. Crystallographic analysis shows HL2 and HL4 coordinate bidentately via the phenolate and methoxy oxygen atoms, while HL3 is bound monodentately through the phenolate oxygen atom. Continuous shape measures depict that the decacoordinate complexes with HL2 and HL4 conform to the sphenocorona and tetradecahedron geometries, respectively, whilst the nona-coordinate Nd(III) complex with HL3 exhibits the muffin geometry. The effect of the ligand substituents and their positions (meta versus para) on the absorption and emission intensities of the complexes is demonstrated. Additionally, the electrochemical behaviour of the o-vanillin-derived Schiff base ligands and their complexes was also investigated, and the results illustrate ligand-based reductions and metal-centred redox potentials that are significantly shifted by the ligand substituents.
- Full Text:
- Date Issued: 2020
- Authors: Pikoli, Sibongile
- Date: 2020
- Subjects: Rare earths , Schiff bases
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/47050 , vital:39778
- Description: This research describes the coordination chemistry of lanthanide complexes with potentially multidentate nitrogen- and oxygen-donor Schiff base derivatives. The studies were performed using various physico-chemical techniques including melting point, IR and NMR spectroscopy, UV-Vis spectroscopy, elemental analyses, conductivity measurements, X-ray crystallography and cyclic voltammetry. The reaction of [Ln(NO3)3·xH2O] (Ln = Nd, Gd, Yb; x = 6 for Nd and Gd, x = 5 for Yb) with the flexible salen-type Schiff base ligand 1,3-bis(o-hydroxybenzylideneamino)propane (H2L1) produced three polynuclear complexes with the general formulae {[Nd(µH2L1)4(NO3)3]·2H2O}n and [Ln(µ-H2L1)2(NO3)6(H2L1)] (Ln = Gd and Yb). Single-crystal Xray crystallography revealed a ten-coordinate polymeric Nd(III) complex that crystallised in the monoclinic space group P21/c, and isostructural nine-coordinate binuclear Gd(III) and Yb(III) complexes (triclinic system, space group P-1). The lanthanide contraction effect is clear across the series. The flexible nature of HL2 results in the self-assembly of the Nd(III) complex in a 1D polymer chain by acting as the bridge between the metal ions. The Nd-Ophenolate bond distances are 2.403(18), 2.463(17), 2.379(17) and 2.367(19) Å and the average Nd-Onitrate bond length is 2.671 Å. Furthermore, the electronic absorption spectra displays 4f→4f transitions solely for the neodymium(III) compound. The syntheses and characterisation of the lanthanide complexes, [La(HL2)3(NO3)3], [Dy(HL2)2(NO3)3] and [Dy(HL2)2Cl3(H2O)]·2CH2Cl2 with the o-vanillin-derived Schiff base ligand 2-methoxy-6-[(E)-(phenylimino)methyl]phenol (HL2) are reported. The nitro-stabilised La(III) and Dy(III) compounds are ten-coordinate with metabidiminished icosahedron and sphenocorona geometries, respectively. Substitution of the nitrate with chloride ions in the starting metal compounds yielded an eight-coordinate Dy(III) complex that adopts the biaugmented trigonal prism geometry. For all three complexes, HL2 exists as a zwitterion that is bound to the metal centre in a mono- and bidentate fashion via the phenolate and methoxy oxygen atoms. The dysprosium(III) chloride complex is stabilised by both intramolecular N−H···O and intermolecular O−H···C1 hydrogen bonds, while the crystal packing of the Ln(III) nitrate complexes is ensured by mainly intramolecular N−H···O hydrogen bonds. Fluorescence studies displayed characteristic Dy(III) f→f transitions (4F9/2 → 6H15/2), which suggest the ligand HL2 is an effective organic antenna to absorb and transfer energy to the dysprosium ion. A series of mononuclear Nd(III) complexes with the Schiff base derivatives 2-methoxy-6-[(E)(phenylimino)methyl]phenol (HL2), 5-methoxy-2-[(E)-(phenylimino)methyl]phenol (HL3) and 2-methoxy-6-{(E)-[(2-methoxyphenyl)imino]methyl}phenol (HL4) yielded structurally diverse complexes defined by the formulae [Nd(HL2)2(NO3)3], [Nd(HL3)3(NO3)3] and [Nd(HL4)2(NO3)3]·CH3OH. Crystallographic analysis shows HL2 and HL4 coordinate bidentately via the phenolate and methoxy oxygen atoms, while HL3 is bound monodentately through the phenolate oxygen atom. Continuous shape measures depict that the decacoordinate complexes with HL2 and HL4 conform to the sphenocorona and tetradecahedron geometries, respectively, whilst the nona-coordinate Nd(III) complex with HL3 exhibits the muffin geometry. The effect of the ligand substituents and their positions (meta versus para) on the absorption and emission intensities of the complexes is demonstrated. Additionally, the electrochemical behaviour of the o-vanillin-derived Schiff base ligands and their complexes was also investigated, and the results illustrate ligand-based reductions and metal-centred redox potentials that are significantly shifted by the ligand substituents.
- Full Text:
- Date Issued: 2020
Synthesis and characterization of MXS (M = Mo & V) and carbon supported MXS nanocomposites as Pt-free counter electrodes for electrode for DSSC application
- Authors: Bede, Asanda
- Date: 2020
- Subjects: Voltammetry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/18599 , vital:42612
- Description: It has been reported that the morphology, crystalline phase composition and electrochemical properties of counter electrode materials such MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials was of considerable importance because it governs the efficiency of many photon assisted chemical and physical reactions in dye sensitized solar cells (DSSCs). The efficiency of DSSCs with composite counter electrode materials is reliant on the stability of the photochemistry reactions which can be optimized by appropriate doping levels of the composite materials. Moreover, the microstructure such as surface area, distribution of the MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials, and the stability of the electrostatic bonds between the MxS (Mo, V) with the carbon support also play a significant role in the performance of the DSSCs. This work evaluates the effect of different mole ratios of the MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials on the morphological, structural and electrochemical properties of the composite materials. MoS2 nanoflakes nanostructures have been synthesized by hydrothermal technique using sodium orthovanadate (Na2MoO4) as precursor. In this work Carbon supported MoS2 NFs have been prepared by physically/chemically mixing different mole ratios of MoS2 NFs with multi-walled carbon nanotubes (MWCNTs) and polyvinylidene in N-methyl-2-pyrrolidinone. The morphological, structural and electrochemical properties of the composite counter electrode materials have been investigated using SEM, XRD FTIR, TEM, RS and CV. SEM analysis has revealed the presence of large MoS2 nanoflakes (NFs) as synthesized. SEM analysis has also revealed significant change in the surface morphology of carbon supported MoS2 composite nanostructures with the change in the mole ratio of the MoS2 NFs and carbon support multi-walled carbon nanotubes. Structural analysis through HRTEM analysis revealed a d-spacing of 0.65 nm with a corresponding (002) lattice plane belonging to a trigonal crystalline phase of MoS2. Also, HRTEM analysis has revealed d-spacing of 0.291 nm corresponding to 002 plane of MWCNTs. Raman spectroscopy has revealed Characteristic Raman vibration frequencies and symmetries at 264.6 cm-1(Eg), 354.2 cm-1 (Ag ) belonging trigonal phase of MoS2 (1T-MoS2). FTIR analysis has revealed a narrow peak at 457.6 cm-1 due Mo-S vibration bond. This observation confirms the success of synthesis of MoS2 nanostructures. Cyclic voltammetry (CV), charge-discharge (CD) and electrochemical impedance spectroscopy (EIS) measurements have revealed that the ratio 6:3:1 have shown to be optimum ratio due to its large reduction rate compared to pristine MoS2 NFs and other carbon supported MoS2 NFs. Calculated Rreduction for the carbon supported MoS2 NFs is the order 3:6:1>1:8:1>6:3:1>8:1:1 indicating the trend of ratio 3:6:1 appeared to have higher reduction rate than the rest of the material and it had far less ΔEpp than the rest of other ratios. All CV curves for both pristine MoS2 NFs and carbon supported MoS2 NFs confirmed a distinct Faradic characteristic. The VS2 nanosheets (NSs) and carbon supported VS2 NSs were also effectively synthesized via hydrothermal method. The SEM micrographs for VS2 NSs and carbon supported VS2 NSs samples reveals level increased. Furthermore, SEM-EDX analysis have confirmed the presence of V and S as well as C and O on carbon supported VS2 nanocomposites, and it clearly shown a gradually blending as the ratios increases. The structural studies through XRD analysis have revealed peaks at 2θ angles of 15.4◦, 28.2◦, 34.2◦, 36.2◦, 43.3◦,48.3◦, 54.4◦, 57.7◦ and 66.2◦ which correspond to the lattice planes (001), (002), (100), (011), (102), (003), (110), (103) and (201) belonging to hexagonal VS2 (H-VS2) crystalline phase as per JCPDS card 36-1139. The HRTEM have revealed that the VS2 NSs have an edge to edge length of ~ 0.294 – 1.248 µm. Also, HRTEM micrographs of VS2 NSs have revealed interplanar d spacing of 0.571 nm belonging to the (001) lattice plane of hexagonal VS2 (H-VS2) structure. FTIR analysis have shown a peak at 558 cm-1 attributed to V-S which is evident that sulfur has bonded with the metal (V) and is in agreement with EDS. CV, CD and EIS measurements have shown that the ratio 1:8:1 is more superior to VS2 NSs and other carbon supported VS2 NSs. Based on Rreduction for the carbon supported nanosheets VS2 nanosheets are ordered as 1:8:1>3:6:1>6:3:1>8:1:1. Carbon supported VS2 NSs of the mole ratio 1:8:1 showed a small resistance of 0.32 Ω. This is further evidence that the carbon supported VS2 NSs of the mole ratio 1:8:1 in addition to revealing excellent catalytic behaviour is also more chemically stable and has good conductivity properties._________
- Full Text:
- Date Issued: 2020
- Authors: Bede, Asanda
- Date: 2020
- Subjects: Voltammetry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/18599 , vital:42612
- Description: It has been reported that the morphology, crystalline phase composition and electrochemical properties of counter electrode materials such MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials was of considerable importance because it governs the efficiency of many photon assisted chemical and physical reactions in dye sensitized solar cells (DSSCs). The efficiency of DSSCs with composite counter electrode materials is reliant on the stability of the photochemistry reactions which can be optimized by appropriate doping levels of the composite materials. Moreover, the microstructure such as surface area, distribution of the MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials, and the stability of the electrostatic bonds between the MxS (Mo, V) with the carbon support also play a significant role in the performance of the DSSCs. This work evaluates the effect of different mole ratios of the MxS (Mo, V) and carbon supported MxS (Mo, V) composite nanomaterials on the morphological, structural and electrochemical properties of the composite materials. MoS2 nanoflakes nanostructures have been synthesized by hydrothermal technique using sodium orthovanadate (Na2MoO4) as precursor. In this work Carbon supported MoS2 NFs have been prepared by physically/chemically mixing different mole ratios of MoS2 NFs with multi-walled carbon nanotubes (MWCNTs) and polyvinylidene in N-methyl-2-pyrrolidinone. The morphological, structural and electrochemical properties of the composite counter electrode materials have been investigated using SEM, XRD FTIR, TEM, RS and CV. SEM analysis has revealed the presence of large MoS2 nanoflakes (NFs) as synthesized. SEM analysis has also revealed significant change in the surface morphology of carbon supported MoS2 composite nanostructures with the change in the mole ratio of the MoS2 NFs and carbon support multi-walled carbon nanotubes. Structural analysis through HRTEM analysis revealed a d-spacing of 0.65 nm with a corresponding (002) lattice plane belonging to a trigonal crystalline phase of MoS2. Also, HRTEM analysis has revealed d-spacing of 0.291 nm corresponding to 002 plane of MWCNTs. Raman spectroscopy has revealed Characteristic Raman vibration frequencies and symmetries at 264.6 cm-1(Eg), 354.2 cm-1 (Ag ) belonging trigonal phase of MoS2 (1T-MoS2). FTIR analysis has revealed a narrow peak at 457.6 cm-1 due Mo-S vibration bond. This observation confirms the success of synthesis of MoS2 nanostructures. Cyclic voltammetry (CV), charge-discharge (CD) and electrochemical impedance spectroscopy (EIS) measurements have revealed that the ratio 6:3:1 have shown to be optimum ratio due to its large reduction rate compared to pristine MoS2 NFs and other carbon supported MoS2 NFs. Calculated Rreduction for the carbon supported MoS2 NFs is the order 3:6:1>1:8:1>6:3:1>8:1:1 indicating the trend of ratio 3:6:1 appeared to have higher reduction rate than the rest of the material and it had far less ΔEpp than the rest of other ratios. All CV curves for both pristine MoS2 NFs and carbon supported MoS2 NFs confirmed a distinct Faradic characteristic. The VS2 nanosheets (NSs) and carbon supported VS2 NSs were also effectively synthesized via hydrothermal method. The SEM micrographs for VS2 NSs and carbon supported VS2 NSs samples reveals level increased. Furthermore, SEM-EDX analysis have confirmed the presence of V and S as well as C and O on carbon supported VS2 nanocomposites, and it clearly shown a gradually blending as the ratios increases. The structural studies through XRD analysis have revealed peaks at 2θ angles of 15.4◦, 28.2◦, 34.2◦, 36.2◦, 43.3◦,48.3◦, 54.4◦, 57.7◦ and 66.2◦ which correspond to the lattice planes (001), (002), (100), (011), (102), (003), (110), (103) and (201) belonging to hexagonal VS2 (H-VS2) crystalline phase as per JCPDS card 36-1139. The HRTEM have revealed that the VS2 NSs have an edge to edge length of ~ 0.294 – 1.248 µm. Also, HRTEM micrographs of VS2 NSs have revealed interplanar d spacing of 0.571 nm belonging to the (001) lattice plane of hexagonal VS2 (H-VS2) structure. FTIR analysis have shown a peak at 558 cm-1 attributed to V-S which is evident that sulfur has bonded with the metal (V) and is in agreement with EDS. CV, CD and EIS measurements have shown that the ratio 1:8:1 is more superior to VS2 NSs and other carbon supported VS2 NSs. Based on Rreduction for the carbon supported nanosheets VS2 nanosheets are ordered as 1:8:1>3:6:1>6:3:1>8:1:1. Carbon supported VS2 NSs of the mole ratio 1:8:1 showed a small resistance of 0.32 Ω. This is further evidence that the carbon supported VS2 NSs of the mole ratio 1:8:1 in addition to revealing excellent catalytic behaviour is also more chemically stable and has good conductivity properties._________
- Full Text:
- Date Issued: 2020
Synthesis of 2,4-Xylidine in continuous flow systems
- Authors: Sagandira, Mellisa Brenda
- Date: 2020
- Subjects: Chemistry, Physical and theoretical -- Research , Chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/49270 , vital:41616
- Description: The continuous flow synthesis of 2,4-xylidine, an important compound in the fine chemical, pharmaceutical as well as the dyes and pigments industries was investigated in this study utilizing 1,3-dimethylbenzene as starting material. The first step involves the highly exothermic nitration of 1,3-dimethylbenzene with mixed acid to afford two nitro isomers, namely 1,3-dimethyl-2-nitrobenzene and 2,4-dimethyl-1-nitrobenzene. Since 2,4-xylidine is the targeted isomer, it is important to get a higher proportion of its nitration precursor 2,4-dimethyl-1-nitrobenzene. A safe and efficient synthesis of 2,4-dimethyl-1-nitrobenzene was therefore developed in continuous flow. This was aided by the micro reactor’s large surface area-to-volume ratio, one of the many features of continuous flow synthesis that enable rapid dissipation of heat allowing exothermic reactions to be conducted safely at ambient or higher temperatures. Two nitration protocols were developed using different micro reactors, a sonicated 1 ml PTFE tube reactor and 2 ml Uniqsis chip reactor. Using a sonicated PTFE tube reactor at room temperature and 15 min residence time, 2,4-dimethyl-1-nitrobenzene was afforded in 100 % conversion and 80 % selectivity. An increase in selectivity to 95 % and 90 % conversion towards 2,4-dimethyl-1-nitrobenzene was achieved using a 2 ml Uniqsis chip reactor at room temperature in 6 min residence time. This was accounted for due to efficient mixing of the two phases brought about by the reactor’s mixing structures, which are designed to create turbulent mixing. Scale-up synthesis of 2,4-dimethyl-1-nitrobenzene was conducted in a 4.5 ml LTF-XXL-ST-04 reactor at room temperature and 6 min residence time affording 90 % conversion and 95 % selectivity with a throughput of 16.6 g/h. Subsequently, reduction of 2,4-dimethyl-1-nitrobenzene to afford 2,4-xylidine was investigated in a 1 ml PTFE tube reactor (0.8 mm ID) using hydrazine in the presence of iron (III) 2,4-pentanedionate catalyst. Maximum conversion of 75 % was achieved at 170 °C in 15 min residence time. A more efficient reduction protocol was developed in a 2.7 ml packed column reactor (10 mm ID) using hydrazine in the presence of Pd/C at 50 °C and 2.5 min residence time affording 94 % conversion towards 2,4-xylidine. Lastly, multistep synthesis of 2,4-xylidine was performed using optimum conditions found using the 2 ml Uniqsis chip reactor and 2.7 ml packed column reactor with the incorporation of a phase separator. Joining the two reactors into a single continuous step afforded 100 % conversion and 95 % selectivity towards 2,4-xylidine with 8 min total residence time. Nitration of other organic compounds followed by reduction of the resultant nitro products was also investigated under respective optimum conditions determined for nitration of 1,3-dimethylbenzene and reduction of 2,4-dimethyl-1-nitrobenzene.
- Full Text:
- Date Issued: 2020
- Authors: Sagandira, Mellisa Brenda
- Date: 2020
- Subjects: Chemistry, Physical and theoretical -- Research , Chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/49270 , vital:41616
- Description: The continuous flow synthesis of 2,4-xylidine, an important compound in the fine chemical, pharmaceutical as well as the dyes and pigments industries was investigated in this study utilizing 1,3-dimethylbenzene as starting material. The first step involves the highly exothermic nitration of 1,3-dimethylbenzene with mixed acid to afford two nitro isomers, namely 1,3-dimethyl-2-nitrobenzene and 2,4-dimethyl-1-nitrobenzene. Since 2,4-xylidine is the targeted isomer, it is important to get a higher proportion of its nitration precursor 2,4-dimethyl-1-nitrobenzene. A safe and efficient synthesis of 2,4-dimethyl-1-nitrobenzene was therefore developed in continuous flow. This was aided by the micro reactor’s large surface area-to-volume ratio, one of the many features of continuous flow synthesis that enable rapid dissipation of heat allowing exothermic reactions to be conducted safely at ambient or higher temperatures. Two nitration protocols were developed using different micro reactors, a sonicated 1 ml PTFE tube reactor and 2 ml Uniqsis chip reactor. Using a sonicated PTFE tube reactor at room temperature and 15 min residence time, 2,4-dimethyl-1-nitrobenzene was afforded in 100 % conversion and 80 % selectivity. An increase in selectivity to 95 % and 90 % conversion towards 2,4-dimethyl-1-nitrobenzene was achieved using a 2 ml Uniqsis chip reactor at room temperature in 6 min residence time. This was accounted for due to efficient mixing of the two phases brought about by the reactor’s mixing structures, which are designed to create turbulent mixing. Scale-up synthesis of 2,4-dimethyl-1-nitrobenzene was conducted in a 4.5 ml LTF-XXL-ST-04 reactor at room temperature and 6 min residence time affording 90 % conversion and 95 % selectivity with a throughput of 16.6 g/h. Subsequently, reduction of 2,4-dimethyl-1-nitrobenzene to afford 2,4-xylidine was investigated in a 1 ml PTFE tube reactor (0.8 mm ID) using hydrazine in the presence of iron (III) 2,4-pentanedionate catalyst. Maximum conversion of 75 % was achieved at 170 °C in 15 min residence time. A more efficient reduction protocol was developed in a 2.7 ml packed column reactor (10 mm ID) using hydrazine in the presence of Pd/C at 50 °C and 2.5 min residence time affording 94 % conversion towards 2,4-xylidine. Lastly, multistep synthesis of 2,4-xylidine was performed using optimum conditions found using the 2 ml Uniqsis chip reactor and 2.7 ml packed column reactor with the incorporation of a phase separator. Joining the two reactors into a single continuous step afforded 100 % conversion and 95 % selectivity towards 2,4-xylidine with 8 min total residence time. Nitration of other organic compounds followed by reduction of the resultant nitro products was also investigated under respective optimum conditions determined for nitration of 1,3-dimethylbenzene and reduction of 2,4-dimethyl-1-nitrobenzene.
- Full Text:
- Date Issued: 2020
Synthesis, crystal structures and characterization of metal–organic framework architectures involving dinuclear copper(ii) benzoic acid derivative complexes
- Authors: Ndima, Lubabalo
- Date: 2020
- Subjects: Supramolecular chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46783 , vital:39657
- Description: Structural copper(II) complexes with aromatic carboxylic acids show a wide spectrum of coordination schemes. Studies of dicopper(II) carboxylates have been associated with a variety of interests for their catalytic, biological and magnetic applications [1]. Various novel dinuclear copper(II) complexes [Cu2(X-benzoate)4L2] with varying substituents (X = CH3, F, Cl, Br, I, NO2 & OCH3) with a desired octahedral geometry have been synthesized. The various complexes were characterized by single crystal X-ray diffraction studies, spectroscopic and thermal methods (UV/Vis, FTIR and TGA, DSC). In most cases, the structures consists of centrosymmetric dimers in which the Cu atoms show a square pyramidal CuO5 coordination. In all cases, dimeric paddle wheel complexes where two copper(II) ions are held together by four benzoates (forming syn– syn bridges between the copper atoms) and the apical coordination site occupied by a solvent ligand (L) or supramolecular linker were obtained. The dimers are extended into 1D chains that result from hydrogen bonding between the coordinated methanol (solvent ligand) on one Cu(II) and the carboxylate group on an adjacent Cu(II) dimer, including interactions arising from various substituents. π–π Stacking interactions are found to be present in the various crystal structures forming 3D supramolecular array. FTIR and UV/Vis spectra of each complex have shown how the resonance and inductive effect of each substituent affects spectral data of each complex.
- Full Text:
- Date Issued: 2020
- Authors: Ndima, Lubabalo
- Date: 2020
- Subjects: Supramolecular chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46783 , vital:39657
- Description: Structural copper(II) complexes with aromatic carboxylic acids show a wide spectrum of coordination schemes. Studies of dicopper(II) carboxylates have been associated with a variety of interests for their catalytic, biological and magnetic applications [1]. Various novel dinuclear copper(II) complexes [Cu2(X-benzoate)4L2] with varying substituents (X = CH3, F, Cl, Br, I, NO2 & OCH3) with a desired octahedral geometry have been synthesized. The various complexes were characterized by single crystal X-ray diffraction studies, spectroscopic and thermal methods (UV/Vis, FTIR and TGA, DSC). In most cases, the structures consists of centrosymmetric dimers in which the Cu atoms show a square pyramidal CuO5 coordination. In all cases, dimeric paddle wheel complexes where two copper(II) ions are held together by four benzoates (forming syn– syn bridges between the copper atoms) and the apical coordination site occupied by a solvent ligand (L) or supramolecular linker were obtained. The dimers are extended into 1D chains that result from hydrogen bonding between the coordinated methanol (solvent ligand) on one Cu(II) and the carboxylate group on an adjacent Cu(II) dimer, including interactions arising from various substituents. π–π Stacking interactions are found to be present in the various crystal structures forming 3D supramolecular array. FTIR and UV/Vis spectra of each complex have shown how the resonance and inductive effect of each substituent affects spectral data of each complex.
- Full Text:
- Date Issued: 2020
Synthesis, photophysicochemical properties and photodynamic therapy activities of indium and zinc phthalocyanines when incorporated into Pluronic polymer micelles
- Authors: Motloung, Banele Mike
- Date: 2020
- Subjects: Indium , Zinc , Phthalocyanines , Polymers , Photochemotherapy , Micelles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167529 , vital:41489
- Description: This thesis reports on the syntheses, photophysicochemical properties and photodynamic therapy activities of symmetrical metallophthalocyanines (MPcs) when alone or when incorporated into Pluronic polymer micelles. The Pcs contain either zinc or indium as central metals and have phenyldiazenylphenoxy, pyridine-2-yloxy and benzo[d]thiazol-2-ylthio as ring substituents. Spectroscopic and microscopic techniques were used to confirm the formation MPcs with micelles. The photophysics and photochemistry of the Pcs were assessed when alone and with micelles. All the studied Pcs showed good photophysicochemical behavior with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yields. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy atom effect obtained from the former. The in vitro dark cytotoxicity and photodynamic therapy of the Pc complexes and conjugates against MCF7 cells was tested. All studied Pc complexes alone and with micelles showed minimum dark toxicity making them applicable for PDT. All complexes displayed good phototoxicity < 50% cell viability (except for complex 2 > 50% cell viability) at concentrations ≤100 μg/mL, however the conjugates showed < 45% cell viability at concentrations ≤ 100 μg/mL, probably due to the small micellar size and EPR effect. The findings from this work show the importance of incorporating photosensitizers such as phthalocyanines into Pluronic polymers micelles and making them water soluble and ultimately improving their photodynamic effect.
- Full Text:
- Date Issued: 2020
- Authors: Motloung, Banele Mike
- Date: 2020
- Subjects: Indium , Zinc , Phthalocyanines , Polymers , Photochemotherapy , Micelles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167529 , vital:41489
- Description: This thesis reports on the syntheses, photophysicochemical properties and photodynamic therapy activities of symmetrical metallophthalocyanines (MPcs) when alone or when incorporated into Pluronic polymer micelles. The Pcs contain either zinc or indium as central metals and have phenyldiazenylphenoxy, pyridine-2-yloxy and benzo[d]thiazol-2-ylthio as ring substituents. Spectroscopic and microscopic techniques were used to confirm the formation MPcs with micelles. The photophysics and photochemistry of the Pcs were assessed when alone and with micelles. All the studied Pcs showed good photophysicochemical behavior with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yields. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy atom effect obtained from the former. The in vitro dark cytotoxicity and photodynamic therapy of the Pc complexes and conjugates against MCF7 cells was tested. All studied Pc complexes alone and with micelles showed minimum dark toxicity making them applicable for PDT. All complexes displayed good phototoxicity < 50% cell viability (except for complex 2 > 50% cell viability) at concentrations ≤100 μg/mL, however the conjugates showed < 45% cell viability at concentrations ≤ 100 μg/mL, probably due to the small micellar size and EPR effect. The findings from this work show the importance of incorporating photosensitizers such as phthalocyanines into Pluronic polymers micelles and making them water soluble and ultimately improving their photodynamic effect.
- Full Text:
- Date Issued: 2020
System analysis of fatigue in pilots and co-pilots executing short-hall flight operations
- Authors: Bennett, Cleo Taylor
- Date: 2020
- Subjects: Air pilots -- Health and hygiene , Fatigue , Work environment -- Psychological aspects , Work environment -- Physiological aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146622 , vital:38543
- Description: Background: This study was conducted as part of Denel’s South African Regional Aircraft (SARA) development project. Regional aircraft have a maximum flight time of 60 minutes. Hence, the study focuses on matters pertaining to the short-haul flight context. Pilot fatigue has been recognised as a safety concern in the aviation industry. It impacts on pilot performance across the board, not least in the short-haul context. However, the specific factors that lead to pilot fatigue in short-haul operations have not been well researched. Research Aim: To identify and examine the factors which influence pilot/co-pilot fatigue in short-haul aviation contexts. Method: Fatigue is multifaceted, and has multiple definitions and descriptions. It is acknowledged as a complex phenomenon, the development of which is dynamically influenced by various factors. Thus, a systems approach based on the work system model by Smith and Carayon-Sainfort (1989) was adopted for this study. A systems analysis was conducted in two parts: 1) a literature analysis, and 2) expert interviews. Results: Both the literature analysis and the interviews indicated that pilot fatigue in short-haul flight operations represent composite system outcomes influenced by various factors. The factors identified were structured (systematised) into categories, namely organizational factors, task-related factors, environmental factors, factors linked to technology and tools, and non-work-related factors specific to the individual pilot. An example of a task-related factor would be the performance by pilots of multiple take-offs and landings; organizational factors include work time arrangements and duty scheduling (e.g. unpredictable schedule, early starts/late finishes, number of flight sectors in a shift, extended working hours, numerous consecutive work days, standby duties, flight, duty and rest limitations (regulations and guidelines); and short turnaround periods); environmental factors might include the small pressurised cockpit environment, movement restriction, very low humidity, low air pressure, vibrations, high noise levels, low light intensity light, and inclement weather); there are many examples of how tools and technology utilized by pilots might affect their fatigue levels; and finally, pilot-specific non-work-related factors would include things like the pilot’s age, health (lifestyle), family stress, work experience and sleep environment. All of these factors were identified during the literature analysis and have a significant bearing on how fatigue could present in short-haul pilots/co-pilots. Other important fatigue-related factors revealed during the expert interviews included, organizational culture, time management, health implications of fatigue, and management of fatigue. Conclusions: Pilot fatigue is a complex and multi-factorial physiological condition. There are many interacting components which contribute to pilot fatigue in short-haul operations. These should be viewed from an integrated perspective and holistic, systems-based approaches should be taken to manage these issues, particularly in the context of short-haul operations. This would optimize pilot performance and well-being and, most importantly, improve the safety of the work environment to enhance overall operation safety. Limitations: The study does not quantify the contributions made to pilot fatigue by the various factors explored. Therefore, care needs to be taken when designing and implementing interventions based on this research.
- Full Text:
- Date Issued: 2020
- Authors: Bennett, Cleo Taylor
- Date: 2020
- Subjects: Air pilots -- Health and hygiene , Fatigue , Work environment -- Psychological aspects , Work environment -- Physiological aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/146622 , vital:38543
- Description: Background: This study was conducted as part of Denel’s South African Regional Aircraft (SARA) development project. Regional aircraft have a maximum flight time of 60 minutes. Hence, the study focuses on matters pertaining to the short-haul flight context. Pilot fatigue has been recognised as a safety concern in the aviation industry. It impacts on pilot performance across the board, not least in the short-haul context. However, the specific factors that lead to pilot fatigue in short-haul operations have not been well researched. Research Aim: To identify and examine the factors which influence pilot/co-pilot fatigue in short-haul aviation contexts. Method: Fatigue is multifaceted, and has multiple definitions and descriptions. It is acknowledged as a complex phenomenon, the development of which is dynamically influenced by various factors. Thus, a systems approach based on the work system model by Smith and Carayon-Sainfort (1989) was adopted for this study. A systems analysis was conducted in two parts: 1) a literature analysis, and 2) expert interviews. Results: Both the literature analysis and the interviews indicated that pilot fatigue in short-haul flight operations represent composite system outcomes influenced by various factors. The factors identified were structured (systematised) into categories, namely organizational factors, task-related factors, environmental factors, factors linked to technology and tools, and non-work-related factors specific to the individual pilot. An example of a task-related factor would be the performance by pilots of multiple take-offs and landings; organizational factors include work time arrangements and duty scheduling (e.g. unpredictable schedule, early starts/late finishes, number of flight sectors in a shift, extended working hours, numerous consecutive work days, standby duties, flight, duty and rest limitations (regulations and guidelines); and short turnaround periods); environmental factors might include the small pressurised cockpit environment, movement restriction, very low humidity, low air pressure, vibrations, high noise levels, low light intensity light, and inclement weather); there are many examples of how tools and technology utilized by pilots might affect their fatigue levels; and finally, pilot-specific non-work-related factors would include things like the pilot’s age, health (lifestyle), family stress, work experience and sleep environment. All of these factors were identified during the literature analysis and have a significant bearing on how fatigue could present in short-haul pilots/co-pilots. Other important fatigue-related factors revealed during the expert interviews included, organizational culture, time management, health implications of fatigue, and management of fatigue. Conclusions: Pilot fatigue is a complex and multi-factorial physiological condition. There are many interacting components which contribute to pilot fatigue in short-haul operations. These should be viewed from an integrated perspective and holistic, systems-based approaches should be taken to manage these issues, particularly in the context of short-haul operations. This would optimize pilot performance and well-being and, most importantly, improve the safety of the work environment to enhance overall operation safety. Limitations: The study does not quantify the contributions made to pilot fatigue by the various factors explored. Therefore, care needs to be taken when designing and implementing interventions based on this research.
- Full Text:
- Date Issued: 2020
Technology in conservation: towards a system for in-field drone detection of invasive vegetation
- James, Katherine Margaret Frances
- Authors: James, Katherine Margaret Frances
- Date: 2020
- Subjects: Drone aircraft in remote sensing , Neural networks (Computer science) , Drone aircraft in remote sensing -- Case studies , Machine learning , Computer vision , Environmental monitoring -- Remote sensing , Invasive plants -- Monitoring
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/143408 , vital:38244
- Description: Remote sensing can assist in monitoring the spread of invasive vegetation. The adoption of camera-carrying unmanned aerial vehicles, commonly referred to as drones, as remote sensing tools has yielded images of higher spatial resolution than traditional techniques. Drones also have the potential to interact with the environment through the delivery of bio-control or herbicide, as seen with their adoption in precision agriculture. Unlike in agricultural applications, however, invasive plants do not have a predictable position relative to each other within the environment. To facilitate the adoption of drones as an environmental monitoring and management tool, drones need to be able to intelligently distinguish between invasive and non-invasive vegetation on the fly. In this thesis, we present the augmentation of a commercially available drone with a deep machine learning model to investigate the viability of differentiating between an invasive shrub and other vegetation. As a case study, this was applied to the shrub genus Hakea, originating in Australia and invasive in several countries including South Africa. However, for this research, the methodology is important, rather than the chosen target plant. A dataset was collected using the available drone and manually annotated to facilitate the supervised training of the model. Two approaches were explored, namely, classification and semantic segmentation. For each of these, several models were trained and evaluated to find the optimal one. The chosen model was then interfaced with the drone via an Android application on a mobile device and its performance was preliminarily evaluated in the field. Based on these findings, refinements were made and thereafter a thorough field evaluation was performed to determine the best conditions for model operation. Results from the classification task show that deep learning models are capable of distinguishing between target and other shrubs in ideal candidate windows. However, classification in this manner is restricted by the proposal of such candidate windows. End-to-end image segmentation using deep learning overcomes this problem, classifying the image in a pixel-wise manner. Furthermore, the use of appropriate loss functions was found to improve model performance. Field tests show that illumination and shadow pose challenges to the model, but that good recall can be achieved when the conditions are ideal. False positive detection remains an issue that could be improved. This approach shows the potential for drones as an environmental monitoring and management tool when coupled with deep machine learning techniques and outlines potential problems that may be encountered.
- Full Text:
- Date Issued: 2020
- Authors: James, Katherine Margaret Frances
- Date: 2020
- Subjects: Drone aircraft in remote sensing , Neural networks (Computer science) , Drone aircraft in remote sensing -- Case studies , Machine learning , Computer vision , Environmental monitoring -- Remote sensing , Invasive plants -- Monitoring
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/143408 , vital:38244
- Description: Remote sensing can assist in monitoring the spread of invasive vegetation. The adoption of camera-carrying unmanned aerial vehicles, commonly referred to as drones, as remote sensing tools has yielded images of higher spatial resolution than traditional techniques. Drones also have the potential to interact with the environment through the delivery of bio-control or herbicide, as seen with their adoption in precision agriculture. Unlike in agricultural applications, however, invasive plants do not have a predictable position relative to each other within the environment. To facilitate the adoption of drones as an environmental monitoring and management tool, drones need to be able to intelligently distinguish between invasive and non-invasive vegetation on the fly. In this thesis, we present the augmentation of a commercially available drone with a deep machine learning model to investigate the viability of differentiating between an invasive shrub and other vegetation. As a case study, this was applied to the shrub genus Hakea, originating in Australia and invasive in several countries including South Africa. However, for this research, the methodology is important, rather than the chosen target plant. A dataset was collected using the available drone and manually annotated to facilitate the supervised training of the model. Two approaches were explored, namely, classification and semantic segmentation. For each of these, several models were trained and evaluated to find the optimal one. The chosen model was then interfaced with the drone via an Android application on a mobile device and its performance was preliminarily evaluated in the field. Based on these findings, refinements were made and thereafter a thorough field evaluation was performed to determine the best conditions for model operation. Results from the classification task show that deep learning models are capable of distinguishing between target and other shrubs in ideal candidate windows. However, classification in this manner is restricted by the proposal of such candidate windows. End-to-end image segmentation using deep learning overcomes this problem, classifying the image in a pixel-wise manner. Furthermore, the use of appropriate loss functions was found to improve model performance. Field tests show that illumination and shadow pose challenges to the model, but that good recall can be achieved when the conditions are ideal. False positive detection remains an issue that could be improved. This approach shows the potential for drones as an environmental monitoring and management tool when coupled with deep machine learning techniques and outlines potential problems that may be encountered.
- Full Text:
- Date Issued: 2020
The application value and most appropriate mapping scales for site classification and evaluation in the South African forest industry
- Authors: Sibhakabhaka, Thembisa
- Date: 2020
- Subjects: Forests and forestry -- South Africa , Forest products industry -- South Africa Geographic information systems
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/49281 , vital:41617
- Description: The South African forest industry is challenged with aspects related to socio-political developments, conflicts with biodiversity values, uncertainties related to climate change, several biotic and abiotic risks, and a limited potential for expansion. For this reason, efficient and optimal land-use is essential, which requires sustainable forest management practices and accurate information and decision support systems. Tree growth patterns, productivity and risks vary according to changes in geology, topography, climate and soil conditions. It is therefore required that forest managers, planners and researchers have a conceptual understanding of the concept of forest site classification and evaluation. This is essential not only for improved levels resilience, but also to maintain a competitive industry in terms of socio-economic and environmental performance. The first chapter of the study aimed to investigate the perceptions and interpretations of a range of representative stakeholders from the forestry industry regarding the value, shortcomings, requirements and design of forest site classification and evaluation systems in use in the local industry. A questionnaire with 16 questions was used for this purpose, and data was analysed using quantitative and qualitative techniques. Results indicated variable levels of understanding amongst respondents of terminology and the nature of systems used in industry. Trends in responses were influenced by the background of stakeholders, the role of individuals in the value chain of forestry as well as past experiences. The perceived importance and value of potential site evaluation applications varied substantially amongst different stakeholders. Results point towards a narrow-focus application for site classification and evaluation systems for site-specific forestry, with a lesser regard with aspects of risk management and environmental performance. Several technical aspects related to site variables, data resolution and scale of presentation were also questioned by participants. Listed priorities for research and development include the integration of site classification and evaluation systems into corporate information systems, modernizing technology, more appropriate site evaluation models, advanced climatic modelling and the development of indices of water and nutrient availability related to forest productivity. There is general agreement for the development of a national forest site classification system. The value of this part of the study lies in the contribution it makes towards our knowledge of stakeholder perceptions regarding site classification and evaluation, as well as the valuable comments made by participants for the refinement of such systems that can serve as indicators for entities involved in education, governance and strategic forest management. The second data chapter of the study involved the development of high-resolution site classification systems in the form of Site Types for two selected study areas in South Africa, one located in Mpumalanga, and the other in the southern Cape. This enabled a comparative analysis with existing low-resolution Land Type classifications that were developed by different authors for the same two study areas, in terms of its reliability, accuracy and general usefulness for applications in the plantation forestry value chain. The comparison of the two types of classification systems revealed that the climate data forming part of the database were of equal accuracy and resolution. However, an obvious difference was detected in the information pertaining to soil in terms of descriptive and spatial data. In the case of both study areas, the Site Type classification systems revealed many soil and geological features that were not indicated by the lower-resolution Land Type systems. Variation in characteristics related to parent material, soil classification, soil depth, intensity of subsoil wetness and soil organic matter were not adequately reflected in these systems. This can potentially have important implications for applications such as species choice, predictions of yield, nutrient optimization, ratings of soil resilience, biodiversity management and evaluations for carbon sequestration potential. The data forming part of this study indicate that although Land Type classification systems can provide valuable support at strategic levels of planning and management, there are several limitations for use at finer scales of resolution. The final chapter of the study includes an investigation and qualitative comparison of the usefulness of Site Type vs. Land Type classification systems, based on existing knowledge in the industry. The two systems are compared in terms of its input towards the following applications: site-species matching, timber yield prediction, site amelioration / site preparation requirements, nutrient management requirements, vegetation management / weed control, management of pests and diseases, determination of risk for soil compaction, soil erosion and nutrient loss, decision making regarding forest engineering operations, prediction of wood / fibre properties, biodiversity management and lastly planning of research activities / priorities. This analysis indicated that applications that require data on only climate and general soil patterns can be supported with equal success by both types of site classification systems. On the other hand, in cases where high-resolution data on site factors are required, Land Type classification systems had numerous shortcomings and received a much lower rating of suitability. The outcome of the study can provide guidance on the development and design of future site classification and evaluation systems for the South African forest industry. High-resolution databases of key site factors should receive priority, together with the development of decision support systems based on causal relationships. This will contribute to the resilience and sustainability of an industry that is increasingly confronted with questions related to the placement, design and management of forest plantations.
- Full Text:
- Date Issued: 2020
- Authors: Sibhakabhaka, Thembisa
- Date: 2020
- Subjects: Forests and forestry -- South Africa , Forest products industry -- South Africa Geographic information systems
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/49281 , vital:41617
- Description: The South African forest industry is challenged with aspects related to socio-political developments, conflicts with biodiversity values, uncertainties related to climate change, several biotic and abiotic risks, and a limited potential for expansion. For this reason, efficient and optimal land-use is essential, which requires sustainable forest management practices and accurate information and decision support systems. Tree growth patterns, productivity and risks vary according to changes in geology, topography, climate and soil conditions. It is therefore required that forest managers, planners and researchers have a conceptual understanding of the concept of forest site classification and evaluation. This is essential not only for improved levels resilience, but also to maintain a competitive industry in terms of socio-economic and environmental performance. The first chapter of the study aimed to investigate the perceptions and interpretations of a range of representative stakeholders from the forestry industry regarding the value, shortcomings, requirements and design of forest site classification and evaluation systems in use in the local industry. A questionnaire with 16 questions was used for this purpose, and data was analysed using quantitative and qualitative techniques. Results indicated variable levels of understanding amongst respondents of terminology and the nature of systems used in industry. Trends in responses were influenced by the background of stakeholders, the role of individuals in the value chain of forestry as well as past experiences. The perceived importance and value of potential site evaluation applications varied substantially amongst different stakeholders. Results point towards a narrow-focus application for site classification and evaluation systems for site-specific forestry, with a lesser regard with aspects of risk management and environmental performance. Several technical aspects related to site variables, data resolution and scale of presentation were also questioned by participants. Listed priorities for research and development include the integration of site classification and evaluation systems into corporate information systems, modernizing technology, more appropriate site evaluation models, advanced climatic modelling and the development of indices of water and nutrient availability related to forest productivity. There is general agreement for the development of a national forest site classification system. The value of this part of the study lies in the contribution it makes towards our knowledge of stakeholder perceptions regarding site classification and evaluation, as well as the valuable comments made by participants for the refinement of such systems that can serve as indicators for entities involved in education, governance and strategic forest management. The second data chapter of the study involved the development of high-resolution site classification systems in the form of Site Types for two selected study areas in South Africa, one located in Mpumalanga, and the other in the southern Cape. This enabled a comparative analysis with existing low-resolution Land Type classifications that were developed by different authors for the same two study areas, in terms of its reliability, accuracy and general usefulness for applications in the plantation forestry value chain. The comparison of the two types of classification systems revealed that the climate data forming part of the database were of equal accuracy and resolution. However, an obvious difference was detected in the information pertaining to soil in terms of descriptive and spatial data. In the case of both study areas, the Site Type classification systems revealed many soil and geological features that were not indicated by the lower-resolution Land Type systems. Variation in characteristics related to parent material, soil classification, soil depth, intensity of subsoil wetness and soil organic matter were not adequately reflected in these systems. This can potentially have important implications for applications such as species choice, predictions of yield, nutrient optimization, ratings of soil resilience, biodiversity management and evaluations for carbon sequestration potential. The data forming part of this study indicate that although Land Type classification systems can provide valuable support at strategic levels of planning and management, there are several limitations for use at finer scales of resolution. The final chapter of the study includes an investigation and qualitative comparison of the usefulness of Site Type vs. Land Type classification systems, based on existing knowledge in the industry. The two systems are compared in terms of its input towards the following applications: site-species matching, timber yield prediction, site amelioration / site preparation requirements, nutrient management requirements, vegetation management / weed control, management of pests and diseases, determination of risk for soil compaction, soil erosion and nutrient loss, decision making regarding forest engineering operations, prediction of wood / fibre properties, biodiversity management and lastly planning of research activities / priorities. This analysis indicated that applications that require data on only climate and general soil patterns can be supported with equal success by both types of site classification systems. On the other hand, in cases where high-resolution data on site factors are required, Land Type classification systems had numerous shortcomings and received a much lower rating of suitability. The outcome of the study can provide guidance on the development and design of future site classification and evaluation systems for the South African forest industry. High-resolution databases of key site factors should receive priority, together with the development of decision support systems based on causal relationships. This will contribute to the resilience and sustainability of an industry that is increasingly confronted with questions related to the placement, design and management of forest plantations.
- Full Text:
- Date Issued: 2020
The effect of age and maturation on anthropometric characteristics and physical abilities of youth South African footballers
- Authors: De Beer, Ashley
- Date: 2020
- Subjects: Soccer -- Physiologial aspects , Soccer players -- South Africa -- Makhanda -- Physiology , Soccer players -- South Africa -- Makhanda -- Psychophysiology , Makana Local Football Association (South Africa)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/141222 , vital:37954
- Description: Currently there is limited research investigating the football related abilities of youth South African individuals. Populations from North and South America, Europe and Asia have been extensively covered in terms of their anthropometric characteristics, physical abilities, technical competency, tactical understanding as well as various personality traits. In describing these details, and especially how each is affected during the ageing and pubertal process, a more informed understanding of the talent development systems is created. A holistic approach to talent development is required to effectively and efficiently produce elite level footballers. An important consideration is the unique socio-economic environment many youth footballers experience which may impact on the talent development process. The present study therefore sought to quantify the anthropometric characteristics and the physical ability level of youth South African footballers from Local Football Association in Makhanda in the Sarah Baartman Region of the Eastern Cape province. In order to achieve this a two-factorial design was used with age and maturity status as independent variables. Anthropometric characteristics were tested by finding the height, weight, body mass index and total fat percentage of participants. Physical ability was determined by results for aerobic capacity, power, acceleration, speed and agility. All tests were football specific and had been widely used in a variety of footballing studies. Additional demographic and socio-economic information was also recorded. A total of 136 participants were placed in their respective Under 11, 13, 15 or Under 19 age groups, while the maturity status of 96 participants were stratified into five distinct categories. Statistical analyses was conducted using p-value significance, with appropriate Tukey post-hoc tests administered when necessary, while effect sizes were calculated using Cohen’s d. Significant changes and practical effect sizes were present for nearly all dependent variables when either stratified by age or by maturity. Total fat percentage was the only dependent variable which was not influenced by either age or maturity. Age and maturity effect sizes for total body fat percentage indicated practical changes present which did not occur during statistical analysis. The present results indicate poor values when compared to normative data or that of other football playing study populations. Further longitudinal research is required to better understand individual growth rates for youth South African footballers, particularly from the Makana region. Implications of the thesis may determine long term development pathways, while the delayed maturity rate is a critical finding which needs to be further researched.
- Full Text:
- Date Issued: 2020
- Authors: De Beer, Ashley
- Date: 2020
- Subjects: Soccer -- Physiologial aspects , Soccer players -- South Africa -- Makhanda -- Physiology , Soccer players -- South Africa -- Makhanda -- Psychophysiology , Makana Local Football Association (South Africa)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/141222 , vital:37954
- Description: Currently there is limited research investigating the football related abilities of youth South African individuals. Populations from North and South America, Europe and Asia have been extensively covered in terms of their anthropometric characteristics, physical abilities, technical competency, tactical understanding as well as various personality traits. In describing these details, and especially how each is affected during the ageing and pubertal process, a more informed understanding of the talent development systems is created. A holistic approach to talent development is required to effectively and efficiently produce elite level footballers. An important consideration is the unique socio-economic environment many youth footballers experience which may impact on the talent development process. The present study therefore sought to quantify the anthropometric characteristics and the physical ability level of youth South African footballers from Local Football Association in Makhanda in the Sarah Baartman Region of the Eastern Cape province. In order to achieve this a two-factorial design was used with age and maturity status as independent variables. Anthropometric characteristics were tested by finding the height, weight, body mass index and total fat percentage of participants. Physical ability was determined by results for aerobic capacity, power, acceleration, speed and agility. All tests were football specific and had been widely used in a variety of footballing studies. Additional demographic and socio-economic information was also recorded. A total of 136 participants were placed in their respective Under 11, 13, 15 or Under 19 age groups, while the maturity status of 96 participants were stratified into five distinct categories. Statistical analyses was conducted using p-value significance, with appropriate Tukey post-hoc tests administered when necessary, while effect sizes were calculated using Cohen’s d. Significant changes and practical effect sizes were present for nearly all dependent variables when either stratified by age or by maturity. Total fat percentage was the only dependent variable which was not influenced by either age or maturity. Age and maturity effect sizes for total body fat percentage indicated practical changes present which did not occur during statistical analysis. The present results indicate poor values when compared to normative data or that of other football playing study populations. Further longitudinal research is required to better understand individual growth rates for youth South African footballers, particularly from the Makana region. Implications of the thesis may determine long term development pathways, while the delayed maturity rate is a critical finding which needs to be further researched.
- Full Text:
- Date Issued: 2020
The effect of alginate supplementation on the growth, feed utilization, digestive enzyme activity levels, and intestinal morphology of juvenile South African abalone (Haliotis midae) fed formulated feeds
- Authors: Tlakedi, Thato
- Date: 2020
- Subjects: Abalones -- Feeding and feeds -- South Africa , Haliotis midae , Abalones -- Digestive organs , Abalones -- Morphology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/145279 , vital:38424
- Description: Alginate occurs abundantly in kelp and while a few studies have quantified the effect of kelp inclusion in formulated Haliotis midae feeds, none have researched the effect of alginate inclusion on the growth of abalone fed this feed. Feeding kelp to cultured abalone affects gut structure and modulates gut bacteria, aiding digestion by upregulating enzyme activity. This farm-based experiment compared the growth, feed utilization, digestive enzyme activity levels and intestinal villi structure between abalone (1-year-old, 10 - 20 mm shell length) fed kelp-supplemented (BK) or alginate-supplemented (BA) diets and abalone fed basal (B) and fresh kelp (K) diets for a period of eight months from June 2017 to February 2018. Growth and enzyme activities were also compared between abalone that experienced dietary changes and abalone that remained on their initial diets. The tested diets were: base diet (B, 34% protein), the same base diet supplemented with fresh minced kelp (0.90% kelp [dry mass, equivalent to 0.20% alginate]; BK), base diet supplemented with sodium alginate (0.20% alginate; BA) and a fresh kelp diet (K). Alginate or kelp inclusion in a formulated feed had no significant effect on the specific growth rates (SGR), linear shell growth rates (LGR), daily percentage feeding rates (PFR), feed conversion ratio (FCR), percentage mass gain (MG) and condition factor (CF) over the eight month trial period, compared to abalone fed the base diet. In October 2017, four months since the start of the trial in June, all the groups fed formulated feeds showed significantly higher average weight gain (8.42 ± 0.72 g to 8.86 ± 0.63 g) compared to the kelp-fed group (6.68 ± 0.43 g). However, no significant differences in the average weight gain were observed between abalone fed kelp and formulated feeds at the end of this study. Furthermore, there were no significant differences in the FCR and PFR between abalone fed the base or alginate diets and abalone fed the fresh kelp diet. However, the SW diet produced significantly lower FCR (1.00 ± 0.13) and PFR (0.78 ± 0.10%) compared to the kelp diet (10.6 ± 1.40% and 8.12 ± 1.01%, respectively). All formulated diets produced non-significant LGR, MG and CF compared to the kelp diet at the end of this study. Enzyme activity levels were compared between abalone fed the test diets in July and August 2017 and February 2018. There were no significant differences in the average alginate lyase specific activity levels between abalone fed formulated diets in July and August 2017. At the end of the trial, however, the alginate diet induced significantly higher alginate lyase specific activity levels (4.89 ± 1.64 mg.mg-1 protein) compared to the base diet (1.57 ± 0.98 mg.mg-1 protein), but showed no significant differences compared to the SW (3.78 ± 0.41 mg.mg-1 protein) and fresh kelp-only diets (4.00 ± 0.62 mg.mg-1 protein). The SW diet showed no significant differences in the alginate lyase specific activity levels compared to the base diet. There were no significant differences in the chymotrypsin activity levels between the test diets throughout this study. Alginate or kelp inclusion also had no significant effect on the intestinal structure compared to the base or fresh kelp diets. This was despite a higher degree of variability in microvilli height and width being observed in abalone fed the kelp-only diet, with microvilli visibly wider and longer than in abalone fed formulated feeds. Switching abalone between some diets significantly affected the average weight gain, MG, FCR and PFR, alginate lyase, chymotrypsin and cellulase activity levels compared to abalone kept on their initial diets. The inclusion levels of kelp and alginate used in this study were likely too low to affect abalone growth as higher inclusion levels, particularly of alginate, have been found to improve fish growth. This study concluded that minced kelp and alginate inclusion in a formulated H. midae diet did not affect the SGR, FCR and intestinal morphology, but significantly affected alginate lyase and chymotrypsin activity levels. Furthermore, changes in growth and digestive enzyme activity levels coincided with dietary changes. Consequently, higher inclusion levels, particularly of sodium alginate, and the effect of dietary changes on abalone growth and digestive enzymes must be investigated in future studies.
- Full Text:
- Date Issued: 2020
- Authors: Tlakedi, Thato
- Date: 2020
- Subjects: Abalones -- Feeding and feeds -- South Africa , Haliotis midae , Abalones -- Digestive organs , Abalones -- Morphology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/145279 , vital:38424
- Description: Alginate occurs abundantly in kelp and while a few studies have quantified the effect of kelp inclusion in formulated Haliotis midae feeds, none have researched the effect of alginate inclusion on the growth of abalone fed this feed. Feeding kelp to cultured abalone affects gut structure and modulates gut bacteria, aiding digestion by upregulating enzyme activity. This farm-based experiment compared the growth, feed utilization, digestive enzyme activity levels and intestinal villi structure between abalone (1-year-old, 10 - 20 mm shell length) fed kelp-supplemented (BK) or alginate-supplemented (BA) diets and abalone fed basal (B) and fresh kelp (K) diets for a period of eight months from June 2017 to February 2018. Growth and enzyme activities were also compared between abalone that experienced dietary changes and abalone that remained on their initial diets. The tested diets were: base diet (B, 34% protein), the same base diet supplemented with fresh minced kelp (0.90% kelp [dry mass, equivalent to 0.20% alginate]; BK), base diet supplemented with sodium alginate (0.20% alginate; BA) and a fresh kelp diet (K). Alginate or kelp inclusion in a formulated feed had no significant effect on the specific growth rates (SGR), linear shell growth rates (LGR), daily percentage feeding rates (PFR), feed conversion ratio (FCR), percentage mass gain (MG) and condition factor (CF) over the eight month trial period, compared to abalone fed the base diet. In October 2017, four months since the start of the trial in June, all the groups fed formulated feeds showed significantly higher average weight gain (8.42 ± 0.72 g to 8.86 ± 0.63 g) compared to the kelp-fed group (6.68 ± 0.43 g). However, no significant differences in the average weight gain were observed between abalone fed kelp and formulated feeds at the end of this study. Furthermore, there were no significant differences in the FCR and PFR between abalone fed the base or alginate diets and abalone fed the fresh kelp diet. However, the SW diet produced significantly lower FCR (1.00 ± 0.13) and PFR (0.78 ± 0.10%) compared to the kelp diet (10.6 ± 1.40% and 8.12 ± 1.01%, respectively). All formulated diets produced non-significant LGR, MG and CF compared to the kelp diet at the end of this study. Enzyme activity levels were compared between abalone fed the test diets in July and August 2017 and February 2018. There were no significant differences in the average alginate lyase specific activity levels between abalone fed formulated diets in July and August 2017. At the end of the trial, however, the alginate diet induced significantly higher alginate lyase specific activity levels (4.89 ± 1.64 mg.mg-1 protein) compared to the base diet (1.57 ± 0.98 mg.mg-1 protein), but showed no significant differences compared to the SW (3.78 ± 0.41 mg.mg-1 protein) and fresh kelp-only diets (4.00 ± 0.62 mg.mg-1 protein). The SW diet showed no significant differences in the alginate lyase specific activity levels compared to the base diet. There were no significant differences in the chymotrypsin activity levels between the test diets throughout this study. Alginate or kelp inclusion also had no significant effect on the intestinal structure compared to the base or fresh kelp diets. This was despite a higher degree of variability in microvilli height and width being observed in abalone fed the kelp-only diet, with microvilli visibly wider and longer than in abalone fed formulated feeds. Switching abalone between some diets significantly affected the average weight gain, MG, FCR and PFR, alginate lyase, chymotrypsin and cellulase activity levels compared to abalone kept on their initial diets. The inclusion levels of kelp and alginate used in this study were likely too low to affect abalone growth as higher inclusion levels, particularly of alginate, have been found to improve fish growth. This study concluded that minced kelp and alginate inclusion in a formulated H. midae diet did not affect the SGR, FCR and intestinal morphology, but significantly affected alginate lyase and chymotrypsin activity levels. Furthermore, changes in growth and digestive enzyme activity levels coincided with dietary changes. Consequently, higher inclusion levels, particularly of sodium alginate, and the effect of dietary changes on abalone growth and digestive enzymes must be investigated in future studies.
- Full Text:
- Date Issued: 2020
The effect of bioslurry effluent on growth and development of swiss chard (beta vulgaris l.)
- Authors: Dumani, Azile
- Date: 2020
- Subjects: Sewage sludge -- Seedlings , Swiss chard -- Seedlings
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/48268 , vital:40837
- Description: Studies were conducted at Döhne Agricultural Development Institute (DADI) (32°31’ 34.077” S; 27°27’ 37.473” E) in Stutterheim, Eastern Cape, South Africa, 2017 and 2018. The objectives of this study were (i) to evaluate the effect of bioslurry effluent on seedling growth of Swiss chard (Beta vulgaris L.), (ii) to study the effect of bioslurry effluent on growth, development and the nutrient content of Swiss chard and (iii) to evaluate the residual effect of bioslurry on biological yield and nutrient content of Swiss chard. Experiment 1 was conducted in a glasshouse using two cultivars (Fordhook giant and Star 1801) seeds planted in 200 cavity trays using Hygromix. The treatments were: control (no fertiliser), 50%Bioslurry, 100%Bioslurry, 200%Bioslurry and the recommended rate of 2:3:4 (30) NPK fertilizer. The experiment was arranged in a randomized complete block design replicated three times. At four weeks after germination, ten seedlings per treatment were destructively sampled randomly to determine shoot height and root length, seedling mass, fresh shoot and fresh root mass, dry mass and nutrient content of leaves. The results showed that fertilization with 100%Bioslurry produced significantly taller seedlings (16.33cm) and shoot height (8.72cm), while the shortest seedlings were obtained from the recommended inorganic fertilizer. Fertilization with 200%Bioslurry and the control treatment produced significantly higher biological yield. compared to other treatments. The interaction between fertilizer treatments, cultivar and season indicated that summer season performed better compared to winter in seedling growth and development, and Fordhook giant fertilized with 100% and 200%Bioslurry was superior compared to Star 1801. Fertilization with 50%Bioslurry resulted in seedlings with higher sodium, while the seedlings grown in the control treatment showed higher copper content. The highest manganese was obtained from the seedlings fertilized with the inorganic fertilizer. In Experiment 2, 10 plots of 4.5m² were established in a greenhouse and were replicated three times, using the same cultivars and fertilizer treatments as in Experiment 1. One seedling was planted per hill at a spacing of 0.25m between plants and 0.5 m between rows and this accommodated 28plants per plot. At 20-day intervals, five plants were randomly selected for data collection until 60 days after transplanting. The cultivar significantly affected growth and biological yield parameters, with Fordhook giant performing better in all the three sampling intervals compared to Star 1801 during summer growing season. Fertilizer application positively affected growth and biological yield parameters and plants treated with 200%Bioslurry and the recommended rate of inorganic fertiliser produced the best results. Experiment 3 was carried out in the same manner as experiment two, except that no fertilizer was applied and the seedlings were planted in corresponding treatment to evaluate the residual effect of bioslurry and inorganic fertilizer. The inorganic fertilizer had the highest residual effect compared to bioslurry. Although not necessarily performing significantly better in terms of the residual effects, the bioslurry showed a good potential as an alternative fertilizer source.
- Full Text:
- Date Issued: 2020
- Authors: Dumani, Azile
- Date: 2020
- Subjects: Sewage sludge -- Seedlings , Swiss chard -- Seedlings
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/48268 , vital:40837
- Description: Studies were conducted at Döhne Agricultural Development Institute (DADI) (32°31’ 34.077” S; 27°27’ 37.473” E) in Stutterheim, Eastern Cape, South Africa, 2017 and 2018. The objectives of this study were (i) to evaluate the effect of bioslurry effluent on seedling growth of Swiss chard (Beta vulgaris L.), (ii) to study the effect of bioslurry effluent on growth, development and the nutrient content of Swiss chard and (iii) to evaluate the residual effect of bioslurry on biological yield and nutrient content of Swiss chard. Experiment 1 was conducted in a glasshouse using two cultivars (Fordhook giant and Star 1801) seeds planted in 200 cavity trays using Hygromix. The treatments were: control (no fertiliser), 50%Bioslurry, 100%Bioslurry, 200%Bioslurry and the recommended rate of 2:3:4 (30) NPK fertilizer. The experiment was arranged in a randomized complete block design replicated three times. At four weeks after germination, ten seedlings per treatment were destructively sampled randomly to determine shoot height and root length, seedling mass, fresh shoot and fresh root mass, dry mass and nutrient content of leaves. The results showed that fertilization with 100%Bioslurry produced significantly taller seedlings (16.33cm) and shoot height (8.72cm), while the shortest seedlings were obtained from the recommended inorganic fertilizer. Fertilization with 200%Bioslurry and the control treatment produced significantly higher biological yield. compared to other treatments. The interaction between fertilizer treatments, cultivar and season indicated that summer season performed better compared to winter in seedling growth and development, and Fordhook giant fertilized with 100% and 200%Bioslurry was superior compared to Star 1801. Fertilization with 50%Bioslurry resulted in seedlings with higher sodium, while the seedlings grown in the control treatment showed higher copper content. The highest manganese was obtained from the seedlings fertilized with the inorganic fertilizer. In Experiment 2, 10 plots of 4.5m² were established in a greenhouse and were replicated three times, using the same cultivars and fertilizer treatments as in Experiment 1. One seedling was planted per hill at a spacing of 0.25m between plants and 0.5 m between rows and this accommodated 28plants per plot. At 20-day intervals, five plants were randomly selected for data collection until 60 days after transplanting. The cultivar significantly affected growth and biological yield parameters, with Fordhook giant performing better in all the three sampling intervals compared to Star 1801 during summer growing season. Fertilizer application positively affected growth and biological yield parameters and plants treated with 200%Bioslurry and the recommended rate of inorganic fertiliser produced the best results. Experiment 3 was carried out in the same manner as experiment two, except that no fertilizer was applied and the seedlings were planted in corresponding treatment to evaluate the residual effect of bioslurry and inorganic fertilizer. The inorganic fertilizer had the highest residual effect compared to bioslurry. Although not necessarily performing significantly better in terms of the residual effects, the bioslurry showed a good potential as an alternative fertilizer source.
- Full Text:
- Date Issued: 2020
The effect of integration of affordable/ low cost housing into urban areas on property values
- Authors: Ngxwashula, Ntomboxolo
- Date: 2020
- Subjects: Housing -- South Africa , Urban poor -- Housing -- South Africa Real property -- Valuation -- South Africa Property
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46838 , vital:39666
- Description: In the recent years in South Africa after the apartheid era, the government has for the past 25 years been embarking on programmes and policy directives to address the past spatial injustices amongst other things that the apartheid government has left the country with. It is clear that some of the apartheid marks are still to this day evident and challenging to resolve. One of the priority government’s projects is to integrate communities without classifying areas with skin colour, income range etc. Since 1994 the government has developed a lot of legislation and policies in favour of spatial integration of low cost housing and affordable housing within the existing urban fabric. According to COGTA. (2016:22) urban areas in South Africa remain marked by profound social divisions, which stem from apartheid planning and, since 1994, have been reinforced by the uneven growth in land values and limited access by the poor to resources. The growth of the black middle class has resulted in more racial mixing in the (previously predominantly white and middle-class) suburbs, however, very little in working-class and poor areas. Furthermore it is argued that the property and land use status quo undermines access to urban opportunity and reinforces the highly inefficient urban sprawl that is characteristic of South Africa’s urban areas. There has been no substantial land reform and restitution, especially in urban areas, in part because of the importance of the formal property market, which increased significantly between 1994 and 2014. While this growth is essential to the health of rates income for municipalities, it has not addressed the issue of well-located, affordable housing and decent shelter for all. Spatial Integration has been implemented in some parts of the country, however it is evident that there is some resistance towards the concept of spatial integration and the most referred to reason for the resistance is that the integration of low cost or social housing into high income areas will decrease the property values of the existing properties in urban areas. This research aims to study and investigate if property values are affected by the inclusion of low cost housing in existing urban areas and further investigate why there is still resistance to the concept of integration and address any underpinning reasons and provide recommendations. In this study the related literature was reviewed and an empirical study was conducted. The empirical study was conducted using a combination of qualitative and quantitative approaches, referred to as Mixed Method. The research involved the use of questionnaires (Multiple Choice questions and Likert Scale format type of questions), semi-structured interviews and observation done by the researcher. The findings suggest that the following variables influence the resistance towards spatial integration of affordable/low cost housing into urban areas: Increased crime rate, Negative impact on property values, Clutch of different cultures, NIMBY Syndrome (Not in my Backyard), and Aesthetics of low cost/ social housing. The findings of this research may be used for a further research for a doctoral research investigating, more comprehensive detail, each of the identified variables in the perceived resistance towards spatial integration into urban areas framework which is apparent in the review of the related literature. In accordance with the results of this study and the testing of the objectives and sub questions, all variables have a positive influence on the perceived effect of spatial integration onto urban areas. Equally, some of the variables are not perceived to have a direct but an indirect relationship with spatial integration. The results of this research confirms this research questions and reveals two important things that, the concept of spatial integration into existing suburbia does have a negative effect on existing middle to high income properties in proximity to the social houses. Secondly the results reveal that concept of spatial integration of social housing into existing suburbia areas does positively affect the property values of the social housing. According to the definition of Property value which refers to the worth of a piece of real estate based on the price that a buyer and seller agree upon, furthermore the value of a property converges at the point where the forces of supply meet the forces of demand. In other words, the value of a property at any given time is determined by what the market will bear. Through this study it has been discovered that although property valuations for residential properties are conducted by means of a Comparative Method, which basically compares similar properties, it is however evident through this research that demand for properties located in areas where spatial integration has been implemented is very low, which leads to property owners desperately reducing their prices just to sell. Therefore this research concludes that spatial integration does have an impact on property values, though it is not a determining factor in the calculation of property value, it has an indirect impact. This study contributed to the South African property development body of knowledge, by determining the factors influencing the continued resistance towards Spatial Integration of affordable/low income housing into existing urban areas on property values.
- Full Text:
- Date Issued: 2020
- Authors: Ngxwashula, Ntomboxolo
- Date: 2020
- Subjects: Housing -- South Africa , Urban poor -- Housing -- South Africa Real property -- Valuation -- South Africa Property
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46838 , vital:39666
- Description: In the recent years in South Africa after the apartheid era, the government has for the past 25 years been embarking on programmes and policy directives to address the past spatial injustices amongst other things that the apartheid government has left the country with. It is clear that some of the apartheid marks are still to this day evident and challenging to resolve. One of the priority government’s projects is to integrate communities without classifying areas with skin colour, income range etc. Since 1994 the government has developed a lot of legislation and policies in favour of spatial integration of low cost housing and affordable housing within the existing urban fabric. According to COGTA. (2016:22) urban areas in South Africa remain marked by profound social divisions, which stem from apartheid planning and, since 1994, have been reinforced by the uneven growth in land values and limited access by the poor to resources. The growth of the black middle class has resulted in more racial mixing in the (previously predominantly white and middle-class) suburbs, however, very little in working-class and poor areas. Furthermore it is argued that the property and land use status quo undermines access to urban opportunity and reinforces the highly inefficient urban sprawl that is characteristic of South Africa’s urban areas. There has been no substantial land reform and restitution, especially in urban areas, in part because of the importance of the formal property market, which increased significantly between 1994 and 2014. While this growth is essential to the health of rates income for municipalities, it has not addressed the issue of well-located, affordable housing and decent shelter for all. Spatial Integration has been implemented in some parts of the country, however it is evident that there is some resistance towards the concept of spatial integration and the most referred to reason for the resistance is that the integration of low cost or social housing into high income areas will decrease the property values of the existing properties in urban areas. This research aims to study and investigate if property values are affected by the inclusion of low cost housing in existing urban areas and further investigate why there is still resistance to the concept of integration and address any underpinning reasons and provide recommendations. In this study the related literature was reviewed and an empirical study was conducted. The empirical study was conducted using a combination of qualitative and quantitative approaches, referred to as Mixed Method. The research involved the use of questionnaires (Multiple Choice questions and Likert Scale format type of questions), semi-structured interviews and observation done by the researcher. The findings suggest that the following variables influence the resistance towards spatial integration of affordable/low cost housing into urban areas: Increased crime rate, Negative impact on property values, Clutch of different cultures, NIMBY Syndrome (Not in my Backyard), and Aesthetics of low cost/ social housing. The findings of this research may be used for a further research for a doctoral research investigating, more comprehensive detail, each of the identified variables in the perceived resistance towards spatial integration into urban areas framework which is apparent in the review of the related literature. In accordance with the results of this study and the testing of the objectives and sub questions, all variables have a positive influence on the perceived effect of spatial integration onto urban areas. Equally, some of the variables are not perceived to have a direct but an indirect relationship with spatial integration. The results of this research confirms this research questions and reveals two important things that, the concept of spatial integration into existing suburbia does have a negative effect on existing middle to high income properties in proximity to the social houses. Secondly the results reveal that concept of spatial integration of social housing into existing suburbia areas does positively affect the property values of the social housing. According to the definition of Property value which refers to the worth of a piece of real estate based on the price that a buyer and seller agree upon, furthermore the value of a property converges at the point where the forces of supply meet the forces of demand. In other words, the value of a property at any given time is determined by what the market will bear. Through this study it has been discovered that although property valuations for residential properties are conducted by means of a Comparative Method, which basically compares similar properties, it is however evident through this research that demand for properties located in areas where spatial integration has been implemented is very low, which leads to property owners desperately reducing their prices just to sell. Therefore this research concludes that spatial integration does have an impact on property values, though it is not a determining factor in the calculation of property value, it has an indirect impact. This study contributed to the South African property development body of knowledge, by determining the factors influencing the continued resistance towards Spatial Integration of affordable/low income housing into existing urban areas on property values.
- Full Text:
- Date Issued: 2020
The effect of muscle type and freezing on the evolution of physico-chemical properties during processing of South African biltong and its final textural properties
- Authors: Ngwendu, Nwabisa
- Date: 2020
- Subjects: Biltong Meat -- Quality -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/12128 , vital:39154
- Description: The study investigated the effect of muscle type and freezing on evaluation of mass transfer during processing physico-chemical of South African biltong and its textural properties. In the first experimental phase of this study, mass transfers, physico-chemical and textural properties (hardness, cohesiveness, springiness, and chewiness) of commercially produced biltong from biceps femoris (BF) and semitendinosus (ST) (n=9) were measured. Biltong was dried at 30oC and 40% relative humidity until it had lost 50% of its initial weight. The initial moisture content, water activity (Aw) of BF muscles (74.3% and 0.992) were significantly lower compared those of ST muscles (75.4% and 0.994%). The fat content of BF (2.3%) muscles was higher (P<0.05) than in ST muscles (1.7%). The salt, weight and water gain for the BF muscle were 2.3%, -2.6% and -7.0% respectively and were significantly higher than those of ST muscles which were 2.1, -0.4 and -4.0, respectively. After drying, the moisture content, Aw, and pH were lower in BF (42.2, 0.886 and 5.29) than those of ST muscles (45.1, 0.911 and 5.42). The salt content was higher (P<0.05) in BF muscle than in ST. Among textural properties, hardness was significantly higher in biltong from the BF (233.0N), while the springiness was significantly lower compared to the ST muscle (178.2N). Therefore, it was concluded that the use of different muscles results in variation of biltong physicochemical characteristics. The second experiment investigated the effect of freezing and muscle type on mass transfers, lipid oxidation, physico-chemical and textural properties of biltong. In this experiment, the iii ST muscles were replaced with semimembranosus (SM) muscles. A total of 12 beef muscles were used, with six BF and six SM muscles frozen in a blast freezer at -40 oC till they reached -20oC; then they were transferred to -20oC for 14 days. The thawing loss for the BF and ST muscles was 1.3 and 2.4% respectively, but there were no significant (P>0.05) differences. The protein and salt content were significantly higher in frozen-thawed (24.3 and 0.13%) muscles than in fresh muscle (20.2 and 0.08%); whereas the fat content and pH were lower (P<0.05) in frozen-thawed (5.36) compared to fresh muscles (5.51). Between muscles, the moisture, salt content, and pH were higher in BF muscles than in SM muscles (73.2, 0.12% and 5.49). Aw was affected by the interaction between freezing and muscle type, with frozenthawed SM having lower Aw (0.990). During salting, salt, weight and water gain did not show any differences (P<0.05). There were no major significant differences after salting. There were lower TBARS and pH in frozen-thawed (1.5mgMDA/kg and 5.15) muscles than in fresh muscles (3.3mgMDA/kg and 5.19) as well as in SM muscles (1.8mgMDA/kg and 5.16) than in BF muscles (3.0mgMDA/kg and 5.19). The moisture was significantly lower in frozen-thawed SM (68.1%) than in fresh SM, BF and frozen-thawed BF (69.3,70.5 and 71.7%) after salting. On the final product, the interaction between muscle type and freezing affected the moisture content, TBARS, chewiness and the springiness of biltong, with the biltong from fresh SM (39.8%) having significantly lower moisture content compared frozenthawed BF and ST muscles as well fresh BF muscles (42.8% in average). The TBARS were higher in biltong from fresh BF muscles (5.1mgMDA/kg) compared to other muscles. Furthermore, the chewiness and springiness were higher (P<0.05) in biltong produced from SM frozen-thawed muscles (327.7N and 1.5). The WBSF was higher in biltong from the BF muscles (108.8N) than in the biltong from SM (80.1) but it was not affected by the freezing effect (P>0.05). Freezing did not show any major differences in biltong. iv The third experiment was conducted to determine the effect of freezing African buffalo carcasses on weight loss during salting, physico-chemical and textural properties of biltong. Five muscles (ST, SM, BF, LTL, and RF) were randomly selected from 30 carcasses (15 frozen-thawed and 15 fresh), cut along the grain, traditionally salted and dried at 26oC till they lost 45-50% of their initial weight. The salting weight loss was higher in frozen-thawed muscles (-1.45%) than in fresh muscles (-0.89%). The freezing treatment affected the physico-chemical properties of the biltong. The biltong produced from frozen-thawed muscles showed significantly higher protein and ash (47.6 and 7.6%) compared to fresh (43.9 and 7.1); whereas the moisture, fat, pH and Aw were lower (43.7, 2.1, 0.870 and 5.30, respectively) compared to those of biltong from fresh muscles (45.5%, 2.9%, 0.890 and 5.38). The moisture, pH and fat content were further affected by muscle type. The interactive effect was observed in salt content, with RF frozen-thawed showing higher salt content (8.2%) compared to all other muscles. The hardness and WBSF were significantly higher (P<0.05) in biltong frozen-thawed (204.1N and 135.0N) than in fresh muscles (146.2N and 113.1N). Moreover, the chewiness and springiness were affected (P<0.05) by muscle type, with RF muscle having higher springiness 0.89 and chewiness 171.1N than all the other muscles. Therefore, it can be concluded that freezing buffalo carcasses significantly influenced the quality characteristics of biltong. The fourth experiment studied the effect of drying methods on physico-chemical properties of traditional biltong produced from African buffalo muscles. The BF and SM muscles were randomly selected from 15 fresh carcasses, cut into strips, salted and divided into two batches per muscle. The first batch of each muscle type was dried in the ambient-air drier at 22oC average and the second batch in the cabinet drier at 26 oC till 45-50% weight loss. No differences (P>0.05) were observed in salting weight loss between the drying method and muscle type. The protein content was significantly higher in SM (46%) muscles compared to v BF (43%) but there was no effect (P>0.05) caused by the drying method. The interactions between the muscle type and drying method affected the fat content, with biltong from airdried BF muscles having significant lower (2.1%) fat content. There were no significant differences in other physico-chemical properties of biltong, with moisture content, salt, ash content, Aw and pH being 45.0%, 5.13%, 44.8%, 7.3%, 2.7%, 0.885 and 5.61 on average, respectively. Overall, the findings of the study show that freezing does have a significant effect on the final quality of biltong. However, it can be concluded that a significant effect on the physico-chemical properties of biltong depends on the changes of mass transfers during salting and drying.
- Full Text:
- Date Issued: 2020
- Authors: Ngwendu, Nwabisa
- Date: 2020
- Subjects: Biltong Meat -- Quality -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/12128 , vital:39154
- Description: The study investigated the effect of muscle type and freezing on evaluation of mass transfer during processing physico-chemical of South African biltong and its textural properties. In the first experimental phase of this study, mass transfers, physico-chemical and textural properties (hardness, cohesiveness, springiness, and chewiness) of commercially produced biltong from biceps femoris (BF) and semitendinosus (ST) (n=9) were measured. Biltong was dried at 30oC and 40% relative humidity until it had lost 50% of its initial weight. The initial moisture content, water activity (Aw) of BF muscles (74.3% and 0.992) were significantly lower compared those of ST muscles (75.4% and 0.994%). The fat content of BF (2.3%) muscles was higher (P<0.05) than in ST muscles (1.7%). The salt, weight and water gain for the BF muscle were 2.3%, -2.6% and -7.0% respectively and were significantly higher than those of ST muscles which were 2.1, -0.4 and -4.0, respectively. After drying, the moisture content, Aw, and pH were lower in BF (42.2, 0.886 and 5.29) than those of ST muscles (45.1, 0.911 and 5.42). The salt content was higher (P<0.05) in BF muscle than in ST. Among textural properties, hardness was significantly higher in biltong from the BF (233.0N), while the springiness was significantly lower compared to the ST muscle (178.2N). Therefore, it was concluded that the use of different muscles results in variation of biltong physicochemical characteristics. The second experiment investigated the effect of freezing and muscle type on mass transfers, lipid oxidation, physico-chemical and textural properties of biltong. In this experiment, the iii ST muscles were replaced with semimembranosus (SM) muscles. A total of 12 beef muscles were used, with six BF and six SM muscles frozen in a blast freezer at -40 oC till they reached -20oC; then they were transferred to -20oC for 14 days. The thawing loss for the BF and ST muscles was 1.3 and 2.4% respectively, but there were no significant (P>0.05) differences. The protein and salt content were significantly higher in frozen-thawed (24.3 and 0.13%) muscles than in fresh muscle (20.2 and 0.08%); whereas the fat content and pH were lower (P<0.05) in frozen-thawed (5.36) compared to fresh muscles (5.51). Between muscles, the moisture, salt content, and pH were higher in BF muscles than in SM muscles (73.2, 0.12% and 5.49). Aw was affected by the interaction between freezing and muscle type, with frozenthawed SM having lower Aw (0.990). During salting, salt, weight and water gain did not show any differences (P<0.05). There were no major significant differences after salting. There were lower TBARS and pH in frozen-thawed (1.5mgMDA/kg and 5.15) muscles than in fresh muscles (3.3mgMDA/kg and 5.19) as well as in SM muscles (1.8mgMDA/kg and 5.16) than in BF muscles (3.0mgMDA/kg and 5.19). The moisture was significantly lower in frozen-thawed SM (68.1%) than in fresh SM, BF and frozen-thawed BF (69.3,70.5 and 71.7%) after salting. On the final product, the interaction between muscle type and freezing affected the moisture content, TBARS, chewiness and the springiness of biltong, with the biltong from fresh SM (39.8%) having significantly lower moisture content compared frozenthawed BF and ST muscles as well fresh BF muscles (42.8% in average). The TBARS were higher in biltong from fresh BF muscles (5.1mgMDA/kg) compared to other muscles. Furthermore, the chewiness and springiness were higher (P<0.05) in biltong produced from SM frozen-thawed muscles (327.7N and 1.5). The WBSF was higher in biltong from the BF muscles (108.8N) than in the biltong from SM (80.1) but it was not affected by the freezing effect (P>0.05). Freezing did not show any major differences in biltong. iv The third experiment was conducted to determine the effect of freezing African buffalo carcasses on weight loss during salting, physico-chemical and textural properties of biltong. Five muscles (ST, SM, BF, LTL, and RF) were randomly selected from 30 carcasses (15 frozen-thawed and 15 fresh), cut along the grain, traditionally salted and dried at 26oC till they lost 45-50% of their initial weight. The salting weight loss was higher in frozen-thawed muscles (-1.45%) than in fresh muscles (-0.89%). The freezing treatment affected the physico-chemical properties of the biltong. The biltong produced from frozen-thawed muscles showed significantly higher protein and ash (47.6 and 7.6%) compared to fresh (43.9 and 7.1); whereas the moisture, fat, pH and Aw were lower (43.7, 2.1, 0.870 and 5.30, respectively) compared to those of biltong from fresh muscles (45.5%, 2.9%, 0.890 and 5.38). The moisture, pH and fat content were further affected by muscle type. The interactive effect was observed in salt content, with RF frozen-thawed showing higher salt content (8.2%) compared to all other muscles. The hardness and WBSF were significantly higher (P<0.05) in biltong frozen-thawed (204.1N and 135.0N) than in fresh muscles (146.2N and 113.1N). Moreover, the chewiness and springiness were affected (P<0.05) by muscle type, with RF muscle having higher springiness 0.89 and chewiness 171.1N than all the other muscles. Therefore, it can be concluded that freezing buffalo carcasses significantly influenced the quality characteristics of biltong. The fourth experiment studied the effect of drying methods on physico-chemical properties of traditional biltong produced from African buffalo muscles. The BF and SM muscles were randomly selected from 15 fresh carcasses, cut into strips, salted and divided into two batches per muscle. The first batch of each muscle type was dried in the ambient-air drier at 22oC average and the second batch in the cabinet drier at 26 oC till 45-50% weight loss. No differences (P>0.05) were observed in salting weight loss between the drying method and muscle type. The protein content was significantly higher in SM (46%) muscles compared to v BF (43%) but there was no effect (P>0.05) caused by the drying method. The interactions between the muscle type and drying method affected the fat content, with biltong from airdried BF muscles having significant lower (2.1%) fat content. There were no significant differences in other physico-chemical properties of biltong, with moisture content, salt, ash content, Aw and pH being 45.0%, 5.13%, 44.8%, 7.3%, 2.7%, 0.885 and 5.61 on average, respectively. Overall, the findings of the study show that freezing does have a significant effect on the final quality of biltong. However, it can be concluded that a significant effect on the physico-chemical properties of biltong depends on the changes of mass transfers during salting and drying.
- Full Text:
- Date Issued: 2020
The effect of waste tyre pyrolysis-derived carbon black on the various properties of natural rubber/styrene-butadiene rubber blends
- Authors: Ketelo, Sisonke
- Date: 2020
- Subjects: Rubber chemistry , Rubber Polymers
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/49115 , vital:41602
- Description: Disposal of waste tyres into landfills is common in developing countries, including South Africa. This behaviour is detrimental to human health as well as other living organisms and the environment itself. There are several recycling methods and processes that have been adopted in various countries to mitigate the situation. These include the recovery of materials such as rubber for re-use; shredding of tyres into small crumb particles for secondary applications in various industries such as civil engineering and the automotive sector; and commonly through heating tyres under a controlled environment to produce oil in a process called pyrolysis. The latter is of interest to the study, with a specific interest in valorization of the process’ resultant char/pyrolysis carbon black. In principle, this study considers the advancement of waste tyre material recovery by finding applications for pyrolysis-derived carbon black (pCB) recovered from waste tyres as it is one of the significant products of pyrolysis. The study involved investigating the effectiveness of pyrolysis-derived carbon black in its ability to improve the properties of natural rubber/styrene-butadiene rubber blends for the conveyor belting industry and other related industries. The pyrolysis-derived carbon black was characterized and compared to commercial grades of carbon blacks on properties such as surface area, thermal stability, heat absorption, structure and morphology using various laboratory techniques such as XRD, XRF, TGA, BET, DSC and SEM. It was found that the properties of the unmodified pCB closely matched those of commercial carbon black grade N660. Through internal mixing, rubber compounds were prepared using 40 phr of pCB and of the selected carbon black grades. Improvements were observed in the mechanical properties of the polymer for application specifications, especially tensile properties and abrasion resistance. Pyrolysis-derived carbon black improved tensile properties to a similar magnitude as a reinforcing carbon black grade and produced similar cure times. Partial replacement of a commercial carbon black grade with pCB of 5 to 20 phr in NR/SBR yielded intermediate results. The unmodified pCB can be used to improve the physical properties of natural rubber/styrene-butadiene rubber blends because it exhibits filler behaviour.
- Full Text:
- Date Issued: 2020
- Authors: Ketelo, Sisonke
- Date: 2020
- Subjects: Rubber chemistry , Rubber Polymers
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/49115 , vital:41602
- Description: Disposal of waste tyres into landfills is common in developing countries, including South Africa. This behaviour is detrimental to human health as well as other living organisms and the environment itself. There are several recycling methods and processes that have been adopted in various countries to mitigate the situation. These include the recovery of materials such as rubber for re-use; shredding of tyres into small crumb particles for secondary applications in various industries such as civil engineering and the automotive sector; and commonly through heating tyres under a controlled environment to produce oil in a process called pyrolysis. The latter is of interest to the study, with a specific interest in valorization of the process’ resultant char/pyrolysis carbon black. In principle, this study considers the advancement of waste tyre material recovery by finding applications for pyrolysis-derived carbon black (pCB) recovered from waste tyres as it is one of the significant products of pyrolysis. The study involved investigating the effectiveness of pyrolysis-derived carbon black in its ability to improve the properties of natural rubber/styrene-butadiene rubber blends for the conveyor belting industry and other related industries. The pyrolysis-derived carbon black was characterized and compared to commercial grades of carbon blacks on properties such as surface area, thermal stability, heat absorption, structure and morphology using various laboratory techniques such as XRD, XRF, TGA, BET, DSC and SEM. It was found that the properties of the unmodified pCB closely matched those of commercial carbon black grade N660. Through internal mixing, rubber compounds were prepared using 40 phr of pCB and of the selected carbon black grades. Improvements were observed in the mechanical properties of the polymer for application specifications, especially tensile properties and abrasion resistance. Pyrolysis-derived carbon black improved tensile properties to a similar magnitude as a reinforcing carbon black grade and produced similar cure times. Partial replacement of a commercial carbon black grade with pCB of 5 to 20 phr in NR/SBR yielded intermediate results. The unmodified pCB can be used to improve the physical properties of natural rubber/styrene-butadiene rubber blends because it exhibits filler behaviour.
- Full Text:
- Date Issued: 2020