Spatial and temporal variations in trophic connectivity within an estuarine environment : benthic-pelagic and terrestrial-aquatic linkages via invertebrates and fishes
- Authors: Bergamino Roman, Leandro
- Date: 2015
- Subjects: Estuarine ecology -- South Africa , Marine invertebrates -- South Africa -- Ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5921 , http://hdl.handle.net/10962/d1017799
- Description: Estuarine ecosystems are among the most biologically productive areas and they provide important ecosystem services such as erosion control, habitat and refugia for several species. These environments are characterized by the presence of a variety of organic matter sources due to their transitional position between rivers and the sea. The biotic compositions can undergo spatial and seasonal changes along the estuary due to the spatial and temporal fluctuations of environmental factors such as salinity, temperature and seston loads. Therefore, the different combinations of biotic and abiotic factors make each estuary a unique ecosystem. Because of this spatial and temporal complexity, the understanding of estuarine food web structure and which factors affect the trophic relationships within the ecosystem through space and time represent challenging tasks. Furthermore, estuaries are under an increasing number of anthropogenic perturbations because of the growing concentration of human populations in coastal areas. Knowledge of ecosystem structure and functioning is essential for effective conservation and management planning of coastal areas.In this dissertation, I combine the utilization of biological tracers to examine spatial and temporal variability in the food web structure within a small temperate and microtidal estuary located in South Africa. To this end, fatty acid profiles and stable isotope signatures were measured in several primary organic matter sources and consumers (including zooplankton, fishes and benthic invertebrates) during four consecutive seasons and in three different estuarine regions: upper, middle, and lower reaches. The three reaches had distinct habitat features of vegetation type and morphology, and in particular the lower reaches were colonized by the marsh grass Spartina maritima. Isotopic mixing models were used to estimate the relative contribution of each food source to the diets of invertebrates and fishes within the estuarine food web. The isotopic and fatty acid data showed similar results. In general, the lower reaches of the estuary were characterized by a higher deposition and assimilation by brachyuran crabs of carbon derived from marsh grass detritus, whiletowards the upper reaches a mixture of microphytobenthos and particulate organic matter (phytoplankton and detritus) was deposited and sustained the pelagic and benthic fauna. The highest deposition and assimilation of marsh grass detritus in the lower reaches of the estuary occurred during periods of low freshwater discharge (autumn and winter). In the upper reaches, microphytobenthos and suspended particulate organic matter were dominant basal food resources for the food web during all seasons. These results indicated that benthic consumers incorporated mainly local carbon sources from their local habitat.To clarify isotopic and fatty acid patterns I examined the trophic behaviour of the sesarmid crab Sesarma catenata through laboratory feeding experiments. Results from these experiments validated that decomposed leaves of riparian trees and the salt marsh plant S. maritima were the preferred food of the sesarmid crabs, potentially due to high bacterial loads. The remaining leaf material not assimilated by crabs, together with faecal material, are likely important subsidies for adjacent environments, hence representing an important energy pathway involving the microbial food chain. Furthermore, this dissertation showed the importance of mobile top predators as vectors energetically connecting distinct food chains within the estuary (i.e. littoral, benthic and pelagic). I concluded that a combination of physical (i.e. patterns of freshwater discharge and estuary morphology) and biological factors (i.e. organism feeding behaviour, mobility, primary productivity, the local vegetation type) influence the pattern of dominant primary organic matter sources, and therefore the food web structure along the estuarine environment. In particular, marsh grass detritus contributed substantially to the diets of estuarine fauna during periods of low freshwater discharge. Given the importance of the salt marsh habitat in providing trophic resources, it is important to preserve this environment to sustain the natural biota and ecosystem functioning.
- Full Text:
- Date Issued: 2015
- Authors: Bergamino Roman, Leandro
- Date: 2015
- Subjects: Estuarine ecology -- South Africa , Marine invertebrates -- South Africa -- Ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5921 , http://hdl.handle.net/10962/d1017799
- Description: Estuarine ecosystems are among the most biologically productive areas and they provide important ecosystem services such as erosion control, habitat and refugia for several species. These environments are characterized by the presence of a variety of organic matter sources due to their transitional position between rivers and the sea. The biotic compositions can undergo spatial and seasonal changes along the estuary due to the spatial and temporal fluctuations of environmental factors such as salinity, temperature and seston loads. Therefore, the different combinations of biotic and abiotic factors make each estuary a unique ecosystem. Because of this spatial and temporal complexity, the understanding of estuarine food web structure and which factors affect the trophic relationships within the ecosystem through space and time represent challenging tasks. Furthermore, estuaries are under an increasing number of anthropogenic perturbations because of the growing concentration of human populations in coastal areas. Knowledge of ecosystem structure and functioning is essential for effective conservation and management planning of coastal areas.In this dissertation, I combine the utilization of biological tracers to examine spatial and temporal variability in the food web structure within a small temperate and microtidal estuary located in South Africa. To this end, fatty acid profiles and stable isotope signatures were measured in several primary organic matter sources and consumers (including zooplankton, fishes and benthic invertebrates) during four consecutive seasons and in three different estuarine regions: upper, middle, and lower reaches. The three reaches had distinct habitat features of vegetation type and morphology, and in particular the lower reaches were colonized by the marsh grass Spartina maritima. Isotopic mixing models were used to estimate the relative contribution of each food source to the diets of invertebrates and fishes within the estuarine food web. The isotopic and fatty acid data showed similar results. In general, the lower reaches of the estuary were characterized by a higher deposition and assimilation by brachyuran crabs of carbon derived from marsh grass detritus, whiletowards the upper reaches a mixture of microphytobenthos and particulate organic matter (phytoplankton and detritus) was deposited and sustained the pelagic and benthic fauna. The highest deposition and assimilation of marsh grass detritus in the lower reaches of the estuary occurred during periods of low freshwater discharge (autumn and winter). In the upper reaches, microphytobenthos and suspended particulate organic matter were dominant basal food resources for the food web during all seasons. These results indicated that benthic consumers incorporated mainly local carbon sources from their local habitat.To clarify isotopic and fatty acid patterns I examined the trophic behaviour of the sesarmid crab Sesarma catenata through laboratory feeding experiments. Results from these experiments validated that decomposed leaves of riparian trees and the salt marsh plant S. maritima were the preferred food of the sesarmid crabs, potentially due to high bacterial loads. The remaining leaf material not assimilated by crabs, together with faecal material, are likely important subsidies for adjacent environments, hence representing an important energy pathway involving the microbial food chain. Furthermore, this dissertation showed the importance of mobile top predators as vectors energetically connecting distinct food chains within the estuary (i.e. littoral, benthic and pelagic). I concluded that a combination of physical (i.e. patterns of freshwater discharge and estuary morphology) and biological factors (i.e. organism feeding behaviour, mobility, primary productivity, the local vegetation type) influence the pattern of dominant primary organic matter sources, and therefore the food web structure along the estuarine environment. In particular, marsh grass detritus contributed substantially to the diets of estuarine fauna during periods of low freshwater discharge. Given the importance of the salt marsh habitat in providing trophic resources, it is important to preserve this environment to sustain the natural biota and ecosystem functioning.
- Full Text:
- Date Issued: 2015
Assessment of the spatial and temporal variations in periphyton communities along a small temperate river system: A multimetric and stable isotope analysis approach
- Dalu, Tatenda, Bere, Taurai, Richoux, Nicole B, Froneman, P William
- Authors: Dalu, Tatenda , Bere, Taurai , Richoux, Nicole B , Froneman, P William
- Date: 2015
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124249 , vital:35580 , https://doi.org/10.1016/j.sajb.2015.05.028
- Description: Periphyton community structure and stable isotope values have been identified as potential indicators of anthropogenic nitrogen pollution, an increasingly important challenge in aquatic systems. The aim of the study was to assess the spatio-temporal changes in periphyton characteristics to identify potential anthropogenic nitrogen pollution sources such as agricultural and sewage discharge within the Kowie River catchment, South Africa. Periphyton was collected once a season from five sites between September 2012 and May 2013. Diversity indices, multimetric and stable isotope analyses were employed for describing the spatial and temporal dynamics of periphyton community assemblages. Water depth, salinity, resistivity, oxygen reduction potential, nitrates, water velocity and conductivity were the major factors affecting periphyton community structure. Eighty-seven periphyton taxa belonging to 43 genera were recorded throughout the study sites and periods. Periphyton species richness, abundance and stable isotope signatures differed significantly among sites but not among seasons. The lower sections of the Kowie River were polluted by anthropogenic sources as indicated by the high periphytic isotopic nitrogen values (7.9–15.2‰) compared to the pristine upstream sites (4–8‰). We recommend that researchers use a combination of community structure and stable isotope measurements to monitor the periphyton in lotic systems.
- Full Text:
- Date Issued: 2015
- Authors: Dalu, Tatenda , Bere, Taurai , Richoux, Nicole B , Froneman, P William
- Date: 2015
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124249 , vital:35580 , https://doi.org/10.1016/j.sajb.2015.05.028
- Description: Periphyton community structure and stable isotope values have been identified as potential indicators of anthropogenic nitrogen pollution, an increasingly important challenge in aquatic systems. The aim of the study was to assess the spatio-temporal changes in periphyton characteristics to identify potential anthropogenic nitrogen pollution sources such as agricultural and sewage discharge within the Kowie River catchment, South Africa. Periphyton was collected once a season from five sites between September 2012 and May 2013. Diversity indices, multimetric and stable isotope analyses were employed for describing the spatial and temporal dynamics of periphyton community assemblages. Water depth, salinity, resistivity, oxygen reduction potential, nitrates, water velocity and conductivity were the major factors affecting periphyton community structure. Eighty-seven periphyton taxa belonging to 43 genera were recorded throughout the study sites and periods. Periphyton species richness, abundance and stable isotope signatures differed significantly among sites but not among seasons. The lower sections of the Kowie River were polluted by anthropogenic sources as indicated by the high periphytic isotopic nitrogen values (7.9–15.2‰) compared to the pristine upstream sites (4–8‰). We recommend that researchers use a combination of community structure and stable isotope measurements to monitor the periphyton in lotic systems.
- Full Text:
- Date Issued: 2015
The diets of co-occuring anurans in a small South African river: assessments using stomach contents, stable isotope ratios and fatty acid profiles
- Authors: Sikutshwa, Likho
- Date: 2015
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54405 , vital:26562
- Description: During their life cycle amphibians change their habitat and feeding, and are important consumers in both terrestrial and aquatic habitats. The trophic ecology of anurans has been studied intensively using gut content analysis, but very little work has been done using biochemical techniques such as stable isotope and fatty acid analyses. These biochemical techniques produce data that allow for additional inferences about the trophic ecology of anurans, as they reveal what the organisms assimilated over time rather than what was recently ingested. The investigation of the feeding ecology and trophic interactions of anurans using gut content analyses together with stable isotope and fatty acid analyses will help us to better understand their ecological roles. The objective of this thesis was to assess the feeding ecology of four anurans (Amietia angolensis, Amietophyrnus rangeri, Strongylopus grayii and Xenopus laevis) in a temperate river using a combination of gut content, stable isotope and fatty acid analyses. Frogs, tadpoles and potential food sources were sampled in two sites (upstream and downstream) in the Kowie River, Eastern Cape Province, South Africa. Gut content analyses identified 147 prey items belonging to 12 prey orders in the stomachs of the sampled specimens. In both A. angolensis and S. grayii the most important prey category was Coleoptera, followed by Hemiptera, Diptera and Hymenoptera at both sites. Aquatic prey items (aquatic hemipterans, chirinomids and blackflies) were the most important food sources for X. laevis (Alimentary Index (IAi) = 6.4; 5.2; 4.2). In Am. rangeri, Hymenoptera was the most important prey category (IAi = 8.3). The trophic niche overlap between A. angolensis and S. grayii was biologically significant (> 0.6), and in the remaining species there was no significant trophic niche overlap. Amietia angolensis showed a larger trophic niche (Levin’s measure; B = 7.7 and Bst = 0.84 downstream, and upstream B = 7.6 (Bst = 0.82) compared to the other species. The gut content analyses showed that frogs feed on a variety of prey items that constitutes food sources from both aquatic and terrestrial habitats. Stable isotopes indicated that aquatic derived sources contributed significantly more towards the diets of X. laevis, A. angolensis tadpoles and S. grayii tadpoles compared with the other anurans, whereas aquatic and terrestrial derived food sources contributed equally to the diets of A. angolensis and S. grayii. Increased trophic positions in A. angolensis and S. grayii occurred throughout their development. The four different species had similar fatty acid profiles in the upstream region, and fairly similar δ13C values, suggesting that they probably consumed similar food. Fatty acid profiles of anurans in the downstream region showed distinct separations among the species. Tadpoles had high levels of diatom-associated fatty acids (20:5ω3; A. angolensis tadpole – 8.4 %, S. grayii tadpole – 9.4 % upstream and downstream; 9.1 and 6.1 % total fatty acids (TFA), respectively). All four species had substantial contributions from bacterial fatty acids, and large proportions of saturated fatty acids (30.6 - 50.0 %) including those with 14 and 18 carbons, indicating that bacterial and detritus food sources played an important role in their diets. The fatty acid profiles revealed high proportions of polyunsaturated fatty acids (PUFAs) and essential fatty acids (EFAs) in all species, indicating a good quality of food and that the quality of food consumed was similar among species. The results demonstrated the usefulness of a combination of traditional techniques (gut content techniques) and biochemical techniques (stable isotopes and fatty acid analysis) for assessing consumption and assimilation. The amphibian assemblages examined derived much of their energy from terrestrial and aquatic sources. This information will allow more precise and comprehensive assessments of trophic interactions in freshwater habitats, along with aiding in future amphibian conservation and management efforts.
- Full Text:
- Date Issued: 2015
- Authors: Sikutshwa, Likho
- Date: 2015
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54405 , vital:26562
- Description: During their life cycle amphibians change their habitat and feeding, and are important consumers in both terrestrial and aquatic habitats. The trophic ecology of anurans has been studied intensively using gut content analysis, but very little work has been done using biochemical techniques such as stable isotope and fatty acid analyses. These biochemical techniques produce data that allow for additional inferences about the trophic ecology of anurans, as they reveal what the organisms assimilated over time rather than what was recently ingested. The investigation of the feeding ecology and trophic interactions of anurans using gut content analyses together with stable isotope and fatty acid analyses will help us to better understand their ecological roles. The objective of this thesis was to assess the feeding ecology of four anurans (Amietia angolensis, Amietophyrnus rangeri, Strongylopus grayii and Xenopus laevis) in a temperate river using a combination of gut content, stable isotope and fatty acid analyses. Frogs, tadpoles and potential food sources were sampled in two sites (upstream and downstream) in the Kowie River, Eastern Cape Province, South Africa. Gut content analyses identified 147 prey items belonging to 12 prey orders in the stomachs of the sampled specimens. In both A. angolensis and S. grayii the most important prey category was Coleoptera, followed by Hemiptera, Diptera and Hymenoptera at both sites. Aquatic prey items (aquatic hemipterans, chirinomids and blackflies) were the most important food sources for X. laevis (Alimentary Index (IAi) = 6.4; 5.2; 4.2). In Am. rangeri, Hymenoptera was the most important prey category (IAi = 8.3). The trophic niche overlap between A. angolensis and S. grayii was biologically significant (> 0.6), and in the remaining species there was no significant trophic niche overlap. Amietia angolensis showed a larger trophic niche (Levin’s measure; B = 7.7 and Bst = 0.84 downstream, and upstream B = 7.6 (Bst = 0.82) compared to the other species. The gut content analyses showed that frogs feed on a variety of prey items that constitutes food sources from both aquatic and terrestrial habitats. Stable isotopes indicated that aquatic derived sources contributed significantly more towards the diets of X. laevis, A. angolensis tadpoles and S. grayii tadpoles compared with the other anurans, whereas aquatic and terrestrial derived food sources contributed equally to the diets of A. angolensis and S. grayii. Increased trophic positions in A. angolensis and S. grayii occurred throughout their development. The four different species had similar fatty acid profiles in the upstream region, and fairly similar δ13C values, suggesting that they probably consumed similar food. Fatty acid profiles of anurans in the downstream region showed distinct separations among the species. Tadpoles had high levels of diatom-associated fatty acids (20:5ω3; A. angolensis tadpole – 8.4 %, S. grayii tadpole – 9.4 % upstream and downstream; 9.1 and 6.1 % total fatty acids (TFA), respectively). All four species had substantial contributions from bacterial fatty acids, and large proportions of saturated fatty acids (30.6 - 50.0 %) including those with 14 and 18 carbons, indicating that bacterial and detritus food sources played an important role in their diets. The fatty acid profiles revealed high proportions of polyunsaturated fatty acids (PUFAs) and essential fatty acids (EFAs) in all species, indicating a good quality of food and that the quality of food consumed was similar among species. The results demonstrated the usefulness of a combination of traditional techniques (gut content techniques) and biochemical techniques (stable isotopes and fatty acid analysis) for assessing consumption and assimilation. The amphibian assemblages examined derived much of their energy from terrestrial and aquatic sources. This information will allow more precise and comprehensive assessments of trophic interactions in freshwater habitats, along with aiding in future amphibian conservation and management efforts.
- Full Text:
- Date Issued: 2015
A re-examination of the type material of Entomoneis paludosa (W Smith) Reimer and its morphology and distribution in African waters
- Richoux, Nicole B, Taylor, J C, Dalu, Tatenda, Froneman, P William
- Authors: Richoux, Nicole B , Taylor, J C , Dalu, Tatenda , Froneman, P William
- Date: 2015
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69179 , vital:29440 , https://doi.org/10.5507/fot.2015.002
- Description: The current study aims to enhance the understanding of the distribution and morphology of the diatom Entomoneis paludosa W Smith 1853 in African waters. The type material of Entomoneis paludosa (W Smith) Reimer was examined using light and scanning electron microscopy and the morphological characters were compared with new specimens sampled from a temperate river in South Africa. The wider distribution of this taxon on the African continent is discussed, and its relationship to water quality variables.
- Full Text:
- Date Issued: 2015
- Authors: Richoux, Nicole B , Taylor, J C , Dalu, Tatenda , Froneman, P William
- Date: 2015
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69179 , vital:29440 , https://doi.org/10.5507/fot.2015.002
- Description: The current study aims to enhance the understanding of the distribution and morphology of the diatom Entomoneis paludosa W Smith 1853 in African waters. The type material of Entomoneis paludosa (W Smith) Reimer was examined using light and scanning electron microscopy and the morphological characters were compared with new specimens sampled from a temperate river in South Africa. The wider distribution of this taxon on the African continent is discussed, and its relationship to water quality variables.
- Full Text:
- Date Issued: 2015
Rhodes University Research Report 2015
- Rhodes University, Gillitt, Tarryn, Goba, Busi, Macgregor, Jill, Roberts, Jaine, Dore, Sally
- Authors: Rhodes University , Gillitt, Tarryn , Goba, Busi , Macgregor, Jill , Roberts, Jaine , Dore, Sally
- Date: 2015
- Language: English
- Type: Text
- Identifier: http://hdl.handle.net/10962/59298 , vital:27546
- Description: From Foreword by Dr Sizwe Mabizela: A further feature of research at Rhodes University has long been international collaborations, many of them responsible for raising the international competitiveness and voice of scholarship involving Rhodes academics and students. In March 2015, Rhodes University became a founder member of the African Research Universities’ Alliance (ARUA), launched at the African Higher Education Summit in Senegal. Leading universities with strong programmes of research and Postgraduate training formed the network of 16 institutions, which aim to bring together intersecting and complementary strengths in the interest of building critical mass in the key development priorities of the African continent. , A publication of the Rhodes University Research Office, compiled and edited by Tarryn Gillitt, Busi Goba, Patricia Jacob, Jill Macgregor and Jaine Roberts. Design & Layout: Sally Dore.
- Full Text:
- Date Issued: 2015
- Authors: Rhodes University , Gillitt, Tarryn , Goba, Busi , Macgregor, Jill , Roberts, Jaine , Dore, Sally
- Date: 2015
- Language: English
- Type: Text
- Identifier: http://hdl.handle.net/10962/59298 , vital:27546
- Description: From Foreword by Dr Sizwe Mabizela: A further feature of research at Rhodes University has long been international collaborations, many of them responsible for raising the international competitiveness and voice of scholarship involving Rhodes academics and students. In March 2015, Rhodes University became a founder member of the African Research Universities’ Alliance (ARUA), launched at the African Higher Education Summit in Senegal. Leading universities with strong programmes of research and Postgraduate training formed the network of 16 institutions, which aim to bring together intersecting and complementary strengths in the interest of building critical mass in the key development priorities of the African continent. , A publication of the Rhodes University Research Office, compiled and edited by Tarryn Gillitt, Busi Goba, Patricia Jacob, Jill Macgregor and Jaine Roberts. Design & Layout: Sally Dore.
- Full Text:
- Date Issued: 2015
Spatio-temporal variation in the phytobenthos and phytoplankton community structure and composition of particulate matter along a river-estuary continuum assessed using microscopic and stable isotope analyses
- Authors: Dalu, Tatenda
- Date: 2015
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/54416 , vital:26563
- Description: Phytoplankton and phytobenthos communities play an important role in lotic systems as primary producers providing essential biomolecules to higher trophic oganisms and are important indicators for environmental or ecological change. In this thesis, field studies (observational and experimental) along a river–estuary continuum were conducted to assess the spatio-temporal variation and development of phytobenthos and phytoplankton communities using a combination of stable isotope and community analyses in a temperate southern African system across four study periods: September (early spring) and November/December (late spring) 2012, and February (summer) and May/June (winter) 2013. Additionally, the sources and composition of the particulate organic matter were also analysed using stable isotope (δ15N and δ13C) analysis. The effects of substrate type and flood occurrence were assessed through experimental studies at an up- and downstream site of the river after a major flood event that occurred between October and November 2012. Common household tiles were used as artificial substrates to study the development/succession of phytobenthos communities after the flood disturbance. Distinct diatom communities were observed between upstream and downstream sites and at each site, community structure changed with time indicating succession. In addition to recording diatom characteristics on three natural substrates, namely; macrophytes, rocks and sediment, artificial substrates observations were also made on three different types of artificial substrates, namely; brick, brown clay and grey clay tiles. The natural (species richness 78) and artificial substrates (sp. richness 93) had different communities with the latter having greater species richness. Common phytobenthos taxa were not restricted to a single substrate but preference was generally high for the artificial substrates, especially brown tiles (mean sp. richness 47). Results of the redundancy analysis (RDA) analysis indicated that ammonium, conductivity, total dissolved solids, salinity, pH, oxygen reduction potential, phosphate and water depth were the major determinants of the phytobenthos composition at the two sites. The spatio–temporal variation of phytoplankton and phytobenthos communities and allochthonous organic matter along the river–estuary continuum was assessed at 8 sites using a combination of community and stable isotope analyses. A total of 178 species belonging to 78 genera were recorded with diatoms being predominant, accounting for 81.9 % of the total abundance. The total chl-a concentration along the river-estuary continuum increased from spring to a high in summer before decreasing to a low in winter. Periphyton communities were observed to be significantly different across sites (p < 0.05) in terms of species richness, abundances and isotopically The high periphytic δ15N values (range 7.9–15.2 ‰) recorded at the downstream sites compared to the pristine upstream sites (δ15N values range 4–7 ‰) suggest nutrient enrichment most likely derived from anthropogenic sources. Overall, our results reveal general patterns of periphyton communities and stable isotopes and provide improved information in the use of periphyton δ15N as an excellent indicator of anthropogenic nitrogen pollution. Ecologists are interested in the factors that control, and the variability in, the contributions of different sources to mixed organic materials traveling through lotic systems. We hypothesized that the source matter fuelling mixed organic pools in a river-estuary continuum varies over space and time, with the upper reaches of a system characterized by allochthonous-dominated material and autochthonous contributions becoming more important in the lower reaches. Samples of the mixed organic pools and allochthonous and autochthonous source materials were collected during the four study periods. The C:N ratios of suspended particulate matter (SPM) collected during summer and winter indicated that the lower reaches of the system had similar organic matter contributions from the freshwater and terrestrial sources. Stable isotope analysis in R revealed that the contributions of autochthonous organic matter were high in SPM along the entire continuum, and aquatic macrophytes were significant contributors to SPM specifically in the upper reaches. The terrestrial leaves made major contributions to the SPM in the middle regions of the system (i.e. downstream sites of the river, particularly in early and late spring). Bulk detritus had large allochthonous matter components in the lower reaches (estuary), and the contributions of aquatic macrophytes and benthic algae to bulk detritus were high (> 50 %) in the upper to middle reaches (river), but low (< 20 %) in the lower reaches (estuary). The current investigation represents the first attempt to assess the validity of the River Continuum Concept (RCC) in a southern African temperate river. The phytoplankton and phytobenthos communities, and chl-a concentration followed a trend similar to that proposed for the river continuum concept (RCC). The middle reaches based on the phytobenthos or phytoplankton communities and chl-a concentrations which were employed as proxies for primary production, were the most productive, while the upper reaches were the least primary productive. The evaluation of organic matter contributions to the SPM and detritus along the river–estuary continuum provided a baseline assessment of the nature and sources of potential food for consumers inhabiting different locations during different times of the year. Incorporating such spatio-temporal variations in SPM and detritus into food web studies will improve our understanding of the flow of carbon through aquatic systems.
- Full Text:
- Date Issued: 2015
- Authors: Dalu, Tatenda
- Date: 2015
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/54416 , vital:26563
- Description: Phytoplankton and phytobenthos communities play an important role in lotic systems as primary producers providing essential biomolecules to higher trophic oganisms and are important indicators for environmental or ecological change. In this thesis, field studies (observational and experimental) along a river–estuary continuum were conducted to assess the spatio-temporal variation and development of phytobenthos and phytoplankton communities using a combination of stable isotope and community analyses in a temperate southern African system across four study periods: September (early spring) and November/December (late spring) 2012, and February (summer) and May/June (winter) 2013. Additionally, the sources and composition of the particulate organic matter were also analysed using stable isotope (δ15N and δ13C) analysis. The effects of substrate type and flood occurrence were assessed through experimental studies at an up- and downstream site of the river after a major flood event that occurred between October and November 2012. Common household tiles were used as artificial substrates to study the development/succession of phytobenthos communities after the flood disturbance. Distinct diatom communities were observed between upstream and downstream sites and at each site, community structure changed with time indicating succession. In addition to recording diatom characteristics on three natural substrates, namely; macrophytes, rocks and sediment, artificial substrates observations were also made on three different types of artificial substrates, namely; brick, brown clay and grey clay tiles. The natural (species richness 78) and artificial substrates (sp. richness 93) had different communities with the latter having greater species richness. Common phytobenthos taxa were not restricted to a single substrate but preference was generally high for the artificial substrates, especially brown tiles (mean sp. richness 47). Results of the redundancy analysis (RDA) analysis indicated that ammonium, conductivity, total dissolved solids, salinity, pH, oxygen reduction potential, phosphate and water depth were the major determinants of the phytobenthos composition at the two sites. The spatio–temporal variation of phytoplankton and phytobenthos communities and allochthonous organic matter along the river–estuary continuum was assessed at 8 sites using a combination of community and stable isotope analyses. A total of 178 species belonging to 78 genera were recorded with diatoms being predominant, accounting for 81.9 % of the total abundance. The total chl-a concentration along the river-estuary continuum increased from spring to a high in summer before decreasing to a low in winter. Periphyton communities were observed to be significantly different across sites (p < 0.05) in terms of species richness, abundances and isotopically The high periphytic δ15N values (range 7.9–15.2 ‰) recorded at the downstream sites compared to the pristine upstream sites (δ15N values range 4–7 ‰) suggest nutrient enrichment most likely derived from anthropogenic sources. Overall, our results reveal general patterns of periphyton communities and stable isotopes and provide improved information in the use of periphyton δ15N as an excellent indicator of anthropogenic nitrogen pollution. Ecologists are interested in the factors that control, and the variability in, the contributions of different sources to mixed organic materials traveling through lotic systems. We hypothesized that the source matter fuelling mixed organic pools in a river-estuary continuum varies over space and time, with the upper reaches of a system characterized by allochthonous-dominated material and autochthonous contributions becoming more important in the lower reaches. Samples of the mixed organic pools and allochthonous and autochthonous source materials were collected during the four study periods. The C:N ratios of suspended particulate matter (SPM) collected during summer and winter indicated that the lower reaches of the system had similar organic matter contributions from the freshwater and terrestrial sources. Stable isotope analysis in R revealed that the contributions of autochthonous organic matter were high in SPM along the entire continuum, and aquatic macrophytes were significant contributors to SPM specifically in the upper reaches. The terrestrial leaves made major contributions to the SPM in the middle regions of the system (i.e. downstream sites of the river, particularly in early and late spring). Bulk detritus had large allochthonous matter components in the lower reaches (estuary), and the contributions of aquatic macrophytes and benthic algae to bulk detritus were high (> 50 %) in the upper to middle reaches (river), but low (< 20 %) in the lower reaches (estuary). The current investigation represents the first attempt to assess the validity of the River Continuum Concept (RCC) in a southern African temperate river. The phytoplankton and phytobenthos communities, and chl-a concentration followed a trend similar to that proposed for the river continuum concept (RCC). The middle reaches based on the phytobenthos or phytoplankton communities and chl-a concentrations which were employed as proxies for primary production, were the most productive, while the upper reaches were the least primary productive. The evaluation of organic matter contributions to the SPM and detritus along the river–estuary continuum provided a baseline assessment of the nature and sources of potential food for consumers inhabiting different locations during different times of the year. Incorporating such spatio-temporal variations in SPM and detritus into food web studies will improve our understanding of the flow of carbon through aquatic systems.
- Full Text:
- Date Issued: 2015
Phytochemical analysis and antibacterial properties of aqueous and ethanol extracts of Brachylaena elliptica (Thurb.) dc. and Brachylaena ilicifolia (Lam.) Phill & Schweick
- Authors: Sagbo, Idowu Jonas
- Date: 2015
- Subjects: Medicinal plants , Traditional medicine , Herbs -- Therapeutic use
- Language: English
- Type: Thesis , Masters , MSc (Biochemistry)
- Identifier: vital:11297 , http://hdl.handle.net/10353/d1021289 , Medicinal plants , Traditional medicine , Herbs -- Therapeutic use
- Description: Resistance of human pathogenic bacterial strains results in selective pressure against known antibiotic. However, plant derived compounds that possess antibacterial potential are currently being investigated for treatment of wound infections in diabetic patients as they are inexpensive and non-toxic. Hence, this dissertation was designed to evaluate two medicinal plants (Brachylaena elliptica and Brachylaena ilicifolia) traditionally used in the treatment of various diseases such as diabetes, and its secondary complications in diabetic patients. The in vitro antioxidant activity of both plants were evaluated using DPPH (1, 1-diphenylhydrazl), ferric reducing power, ABTS (2, 2’-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid), NO (nitric oxide) and H2O2 (hydrogen peroxide) techniques. The antibacterial test and Minimum inhibitory concentration (MIC) was determined by agar dilution method against 5 bacteria strains (Pseudomonas aeruginosa, Staphylococcus aureus, Streptococcus pyogene, Proteus vulgaris and Proteus mirabilis) infecting wounds in diabetic patients using amoxicillin and ciprofloxacin as positive control. The phytochemical analyses were assessed using standard published methods. Identification of bioactive components in essential oils of both plants were assessed using GCMS. The aqueous and ethanol extracts of both plants were also evaluated to identify bioactive components using LC-MS. The results of the phytochemical analysis revealed the presence of phenols, tannins, flavanoids, flavanols, proanthocyanidins, saponins and alkaloids in both plants. Both plants indicated strong antioxidant activities which might be due to the presence of bioactive compounds. The aqueous and ethanol leaf extracts of both plants demonstrated appreciable broad spectrum activities against these wound pathogens with MIC ranging between 5 and 0.3 mg/ml. The GC-MS analysis of the essential oils of both plants revealed the presence of monoterpenes, oxygenated sesquiterpenes, phenolics and esters. The LC-MS analysis of the aqueous and ethanol leaf extracts of both plants showed that both plants are rich in alkaloids, terpenes, terpenoids, monoterpernoids, and flavanoids. Conclusively, this study has partially justified the ethnomedicinal use of B. elliptica and B.licifolia leaves for the treatment of various diseases, including diabetes and wound infections caused by bacteria in diabetic patients. These may be attributed to the presence of antioxidant compound such as phenols, flavanoids, saponins, tannins, alkaloids and other phytochemical compounds.
- Full Text:
- Date Issued: 2015
- Authors: Sagbo, Idowu Jonas
- Date: 2015
- Subjects: Medicinal plants , Traditional medicine , Herbs -- Therapeutic use
- Language: English
- Type: Thesis , Masters , MSc (Biochemistry)
- Identifier: vital:11297 , http://hdl.handle.net/10353/d1021289 , Medicinal plants , Traditional medicine , Herbs -- Therapeutic use
- Description: Resistance of human pathogenic bacterial strains results in selective pressure against known antibiotic. However, plant derived compounds that possess antibacterial potential are currently being investigated for treatment of wound infections in diabetic patients as they are inexpensive and non-toxic. Hence, this dissertation was designed to evaluate two medicinal plants (Brachylaena elliptica and Brachylaena ilicifolia) traditionally used in the treatment of various diseases such as diabetes, and its secondary complications in diabetic patients. The in vitro antioxidant activity of both plants were evaluated using DPPH (1, 1-diphenylhydrazl), ferric reducing power, ABTS (2, 2’-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid), NO (nitric oxide) and H2O2 (hydrogen peroxide) techniques. The antibacterial test and Minimum inhibitory concentration (MIC) was determined by agar dilution method against 5 bacteria strains (Pseudomonas aeruginosa, Staphylococcus aureus, Streptococcus pyogene, Proteus vulgaris and Proteus mirabilis) infecting wounds in diabetic patients using amoxicillin and ciprofloxacin as positive control. The phytochemical analyses were assessed using standard published methods. Identification of bioactive components in essential oils of both plants were assessed using GCMS. The aqueous and ethanol extracts of both plants were also evaluated to identify bioactive components using LC-MS. The results of the phytochemical analysis revealed the presence of phenols, tannins, flavanoids, flavanols, proanthocyanidins, saponins and alkaloids in both plants. Both plants indicated strong antioxidant activities which might be due to the presence of bioactive compounds. The aqueous and ethanol leaf extracts of both plants demonstrated appreciable broad spectrum activities against these wound pathogens with MIC ranging between 5 and 0.3 mg/ml. The GC-MS analysis of the essential oils of both plants revealed the presence of monoterpenes, oxygenated sesquiterpenes, phenolics and esters. The LC-MS analysis of the aqueous and ethanol leaf extracts of both plants showed that both plants are rich in alkaloids, terpenes, terpenoids, monoterpernoids, and flavanoids. Conclusively, this study has partially justified the ethnomedicinal use of B. elliptica and B.licifolia leaves for the treatment of various diseases, including diabetes and wound infections caused by bacteria in diabetic patients. These may be attributed to the presence of antioxidant compound such as phenols, flavanoids, saponins, tannins, alkaloids and other phytochemical compounds.
- Full Text:
- Date Issued: 2015
The quantification of fucoxanthin from selected South African marine brown algae (Phaeophyta) using HPLC-UV/Vis
- Authors: Mubaiwa, Byron Tawanda
- Date: 2015
- Subjects: Marine algae , Brown algae , High performance liquid chromatography , Functional foods , Xanthophylls , Carotenoids , Extraction (Chemistry)
- Language: English
- Type: Thesis , Masters , MPharm
- Identifier: vital:3868 , http://hdl.handle.net/10962/d1017879
- Description: Marine brown algae (seaweeds) are a rich source of fucoxanthin, a xanthophyll carotenoid that is naturally, an accessory pigment in the process of photosynthesis of sea vegetation such as Sargassum incisifolium. Fucoxanthin has been exploited by nutraceutical companies for its anti-obesity effects that has resulted in an increase of seaweed slimming preparations such as FucoThin™. The field is getting widespread consumer attention as interest in fucoxanthin has also transcended to its widespread biological potential which include cytotoxicity, anti-diabetic, anti-oxidant, anti-inflammatory and anti-plasmodium effects. We therefore wanted to identify a reliable source(s) of fucoxanthin from diverse samples of South African marine brown algae in order to explore our medicinal chemistry interests around the cytotoxicity and anti-malarial potential of fucoxanthin. A known source, Sargassum incisifolium, was used to isolate (maceration in CH₂Cl₂/MeOH at 35 °C followed by a hexane/EtOAc step gradient silica column of the crude extract and reversed phase semi-prep HPLC) and characterize (1D and 2D NMR) fucoxanthin (reference standard) in order to develop an analytical method for its determination in selected diverse brown algae commonly found in South Africa. The HPLC [Column: Phenomenex® Synergi™ (250 x 3.0 mm i.d); Mobile phase: ACN/H2O (95:5)] method developed for this analysis was validated according the guidelines set by the International Conference on Harmonization (ICH). Fifteen species were then assessed for fucoxanthin content (μg/g of dried weight) using the developed method. Stability studies on fucoxanthin were also carried out to assess photo- and pH degradation of fucoxanthin. Zonaria subarticulata (KOS130226-18) from Kenton-On-Sea beach and Sargassum incisifolium (PA130427-1) from Port Alfred beach were found to be the highest producers of fucoxanthin with 0.50 mg/g and 0.45 mg/g dried weight respectively. Fucoxanthin was found to be both photo-labile and sensitive to both acidic and basic pH environments. However, the pigment was more photostable in pure as opposed to extract form and also showed to be more stable at pH 10.0. Our findings show that Z. subarticulata and S. incisifolium could be reliable sources of fucoxanthin and can be considered as the algae to use in optimized extraction procedures in further studies. Also, when working with fucoxanthin, it is important to protect it from light. Any consideration of taking fucoxanthin preparation orally (as a nutraceutical) should consider protecting the active from the harsh conditions of the gastrointestinal tract. Any upscale production of fucoxanthin from seaweed should consider variations such as geographical, seasonal, lifecycle stage, etc. of identified algae as these may be important factors in obtaining effective concentrations of fucoxanthin.
- Full Text:
- Date Issued: 2015
- Authors: Mubaiwa, Byron Tawanda
- Date: 2015
- Subjects: Marine algae , Brown algae , High performance liquid chromatography , Functional foods , Xanthophylls , Carotenoids , Extraction (Chemistry)
- Language: English
- Type: Thesis , Masters , MPharm
- Identifier: vital:3868 , http://hdl.handle.net/10962/d1017879
- Description: Marine brown algae (seaweeds) are a rich source of fucoxanthin, a xanthophyll carotenoid that is naturally, an accessory pigment in the process of photosynthesis of sea vegetation such as Sargassum incisifolium. Fucoxanthin has been exploited by nutraceutical companies for its anti-obesity effects that has resulted in an increase of seaweed slimming preparations such as FucoThin™. The field is getting widespread consumer attention as interest in fucoxanthin has also transcended to its widespread biological potential which include cytotoxicity, anti-diabetic, anti-oxidant, anti-inflammatory and anti-plasmodium effects. We therefore wanted to identify a reliable source(s) of fucoxanthin from diverse samples of South African marine brown algae in order to explore our medicinal chemistry interests around the cytotoxicity and anti-malarial potential of fucoxanthin. A known source, Sargassum incisifolium, was used to isolate (maceration in CH₂Cl₂/MeOH at 35 °C followed by a hexane/EtOAc step gradient silica column of the crude extract and reversed phase semi-prep HPLC) and characterize (1D and 2D NMR) fucoxanthin (reference standard) in order to develop an analytical method for its determination in selected diverse brown algae commonly found in South Africa. The HPLC [Column: Phenomenex® Synergi™ (250 x 3.0 mm i.d); Mobile phase: ACN/H2O (95:5)] method developed for this analysis was validated according the guidelines set by the International Conference on Harmonization (ICH). Fifteen species were then assessed for fucoxanthin content (μg/g of dried weight) using the developed method. Stability studies on fucoxanthin were also carried out to assess photo- and pH degradation of fucoxanthin. Zonaria subarticulata (KOS130226-18) from Kenton-On-Sea beach and Sargassum incisifolium (PA130427-1) from Port Alfred beach were found to be the highest producers of fucoxanthin with 0.50 mg/g and 0.45 mg/g dried weight respectively. Fucoxanthin was found to be both photo-labile and sensitive to both acidic and basic pH environments. However, the pigment was more photostable in pure as opposed to extract form and also showed to be more stable at pH 10.0. Our findings show that Z. subarticulata and S. incisifolium could be reliable sources of fucoxanthin and can be considered as the algae to use in optimized extraction procedures in further studies. Also, when working with fucoxanthin, it is important to protect it from light. Any consideration of taking fucoxanthin preparation orally (as a nutraceutical) should consider protecting the active from the harsh conditions of the gastrointestinal tract. Any upscale production of fucoxanthin from seaweed should consider variations such as geographical, seasonal, lifecycle stage, etc. of identified algae as these may be important factors in obtaining effective concentrations of fucoxanthin.
- Full Text:
- Date Issued: 2015
Rhodes University Graduation Ceremony 2015
- Authors: Rhodes University
- Date: 2015
- Language: English
- Type: Text
- Identifier: vital:8149 , http://hdl.handle.net/10962/d1019888
- Description: Rhodes University Graduation Ceremonies 2015 [at] 1820 Settlers National Monument Thursday, 09 April at 10.00 & 17:00 [and] Friday, 10 April at 10:00; 14:30 & 18:00 [and] Saturday, 11 April at 10:00 , Rhodes University Awards, Scholarships,Bursaries and Prizes 2015
- Full Text:
- Date Issued: 2015
- Authors: Rhodes University
- Date: 2015
- Language: English
- Type: Text
- Identifier: vital:8149 , http://hdl.handle.net/10962/d1019888
- Description: Rhodes University Graduation Ceremonies 2015 [at] 1820 Settlers National Monument Thursday, 09 April at 10.00 & 17:00 [and] Friday, 10 April at 10:00; 14:30 & 18:00 [and] Saturday, 11 April at 10:00 , Rhodes University Awards, Scholarships,Bursaries and Prizes 2015
- Full Text:
- Date Issued: 2015
Synthesis and biological evaluation of truncated sarganaphthoquinoic acid derivatives as Hsp90 inhibitors
- Authors: Chiwakata, Maynard T
- Date: 2015
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64708 , vital:28594
- Description: Hsp90 inhibition has been at the centre of attention in current research due to the possibility of “cracking down” on the entire process leading to the development of malignant cancers. Small underlying principles common in all types of cancers have been determined that govern the transformation of normal human cells into cancerous cells, with all relying on the ATPase activity of Hsp90 protein. Hsp90 protein is therefore an attractive drug target that if successfully inhibited can result in the remission of cancer tumours by one form of treatment. To date, no Hsp90 inhibitor has been sanctioned for cancer treatment as most are still in clinical development. Our research was therefore inspired by reports that indicated the potential of quinones / naphthoquinones to act as Hsp90 inhibitors. Preliminary results of a few selected marine natural product quinone systems i.e. sargaquinoic acid (SQA) (2.47) and lapachol (3.6) showed moderate cytotoxicity and weak interactions with the Hsp90 molecular chaperone, and evidence suggested C-terminal binding of these molecules. No correlation has been determined yet between cytotoxicity and Hsp90 inhibition, hence we aimed to develop natural product inspired molecules that exhibit both cytotoxic and Hsp90 inhibition properties. Due to limited amounts of the natural product that can be acquired from natural sources, synthetic analogues were opted for. Isolation of a few selected quinones was conducted to have material that could be used in biological assays. For structural modifications, a series of truncated naphthoquinone systems were prepared adopting the sarganaphthoquinoic acid (3.5) scaffold. The naphthoquinones were prepared via Diels-Alder reactions of relevant benzoquinones with myrcene, followed by aromatization reactions using MnO2. Various alkyl and aryl amines were then coupled to the C-2/3 position of the naphthoquinone using Michael’s addition reactions. Tricyclic naphthoquinones were also synthesized from reactions with hypotaurine and citral. Design of the analogues incorporated functionalities from known Hsp90 inhibitors e.g. geldanamycin (2.28) and its analogues. Preliminary results obtained showed that coupling of naphthoquinones with aryl-amines resulted in the most cytotoxic compounds (4.14-4.19) with IC50 values as low as 0.3 μM against Hs578T breast cancer carcinoma (triple negative). Most of the alkyl amines (4.20-4.25) had IC50 values greater than 50 μM except for 4.20 and 4.21 that showed IC50 values of 7.6 μM and 2.6 μM respectively. Tricyclic naphthoquinones (4.28-4.29) showed moderate cytotoxic activity of approximately 10 μM. Hsp90 inhibition was assessed by client protein degradation assays, of which SQA (2.47), showed the best Hsp90 inhibition properties, followed by compound 4.20. The most cytotoxic arylamino-naphthoquinone (4.16) and tricyclic naphthoquinones (4.28-4.29) showed only moderate inhibition. None of the compounds led to Hsp70 induction, suggesting possible binding to the C-terminus of Hsp90. Interactions at the binding site were assessed by molecular docking studies and saturation transfer difference (STD) NMR. Docking studies were conducted on the N-terminus of Hsp90 and better binding was observed for arylamino naphthoquinones (4.14-4.19) than for other series of compounds. Unfortunately, the co-crystal structure for the C-terminus of Hsp90 is unavailable, hence docking study comparisons on both domains could not be conducted. However, STD NMR offered a platform to assess binding interactions between the naphthoquinones and the N- or C-terminal domains of Hsp90. However no interactions were observed at both the N- and C- termini of Hsp90 due to either weak binding of ligands to the protein or poor water solubility of the ligands. From these preliminary results, naphthoquinones bind to Hsp90 protein but conclusive remarks to which terminal domain they bind to could not be made. The best candidate from amongst the series of naphthoquinones prepared that showed moderate cytotoxicity and promising Hsp90 inhibition was compound 4.20. We therefore succeeded in developing a new series of naphthoquinones that possess moderate cytotoxicity and show Hsp90 inhibition.
- Full Text:
- Date Issued: 2015
- Authors: Chiwakata, Maynard T
- Date: 2015
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64708 , vital:28594
- Description: Hsp90 inhibition has been at the centre of attention in current research due to the possibility of “cracking down” on the entire process leading to the development of malignant cancers. Small underlying principles common in all types of cancers have been determined that govern the transformation of normal human cells into cancerous cells, with all relying on the ATPase activity of Hsp90 protein. Hsp90 protein is therefore an attractive drug target that if successfully inhibited can result in the remission of cancer tumours by one form of treatment. To date, no Hsp90 inhibitor has been sanctioned for cancer treatment as most are still in clinical development. Our research was therefore inspired by reports that indicated the potential of quinones / naphthoquinones to act as Hsp90 inhibitors. Preliminary results of a few selected marine natural product quinone systems i.e. sargaquinoic acid (SQA) (2.47) and lapachol (3.6) showed moderate cytotoxicity and weak interactions with the Hsp90 molecular chaperone, and evidence suggested C-terminal binding of these molecules. No correlation has been determined yet between cytotoxicity and Hsp90 inhibition, hence we aimed to develop natural product inspired molecules that exhibit both cytotoxic and Hsp90 inhibition properties. Due to limited amounts of the natural product that can be acquired from natural sources, synthetic analogues were opted for. Isolation of a few selected quinones was conducted to have material that could be used in biological assays. For structural modifications, a series of truncated naphthoquinone systems were prepared adopting the sarganaphthoquinoic acid (3.5) scaffold. The naphthoquinones were prepared via Diels-Alder reactions of relevant benzoquinones with myrcene, followed by aromatization reactions using MnO2. Various alkyl and aryl amines were then coupled to the C-2/3 position of the naphthoquinone using Michael’s addition reactions. Tricyclic naphthoquinones were also synthesized from reactions with hypotaurine and citral. Design of the analogues incorporated functionalities from known Hsp90 inhibitors e.g. geldanamycin (2.28) and its analogues. Preliminary results obtained showed that coupling of naphthoquinones with aryl-amines resulted in the most cytotoxic compounds (4.14-4.19) with IC50 values as low as 0.3 μM against Hs578T breast cancer carcinoma (triple negative). Most of the alkyl amines (4.20-4.25) had IC50 values greater than 50 μM except for 4.20 and 4.21 that showed IC50 values of 7.6 μM and 2.6 μM respectively. Tricyclic naphthoquinones (4.28-4.29) showed moderate cytotoxic activity of approximately 10 μM. Hsp90 inhibition was assessed by client protein degradation assays, of which SQA (2.47), showed the best Hsp90 inhibition properties, followed by compound 4.20. The most cytotoxic arylamino-naphthoquinone (4.16) and tricyclic naphthoquinones (4.28-4.29) showed only moderate inhibition. None of the compounds led to Hsp70 induction, suggesting possible binding to the C-terminus of Hsp90. Interactions at the binding site were assessed by molecular docking studies and saturation transfer difference (STD) NMR. Docking studies were conducted on the N-terminus of Hsp90 and better binding was observed for arylamino naphthoquinones (4.14-4.19) than for other series of compounds. Unfortunately, the co-crystal structure for the C-terminus of Hsp90 is unavailable, hence docking study comparisons on both domains could not be conducted. However, STD NMR offered a platform to assess binding interactions between the naphthoquinones and the N- or C-terminal domains of Hsp90. However no interactions were observed at both the N- and C- termini of Hsp90 due to either weak binding of ligands to the protein or poor water solubility of the ligands. From these preliminary results, naphthoquinones bind to Hsp90 protein but conclusive remarks to which terminal domain they bind to could not be made. The best candidate from amongst the series of naphthoquinones prepared that showed moderate cytotoxicity and promising Hsp90 inhibition was compound 4.20. We therefore succeeded in developing a new series of naphthoquinones that possess moderate cytotoxicity and show Hsp90 inhibition.
- Full Text:
- Date Issued: 2015
Phthalocyanine-nanoparticle conjugates for photodynamic therapy of cancer and phototransformation of organic pollutants
- Authors: Khoza, Phindile Brenda
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Photochemotherapy , Cancer -- Chemotherapy , Zinc oxide , Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4538 , http://hdl.handle.net/10962/d1017918
- Description: The synthesis and extensive spectroscopical characterization of novel phthalocyanines are reported. The new compounds were characterized by elemental analysis, FT-IR, ¹HNMR, mass spectrometry and UV–Vis spectroscopy. The new phthalocyanines showed remarkable photophysicochemical behaviour. The novel phthalocyanines were then conjugated to nanoparticles, silver and ZnO. The coupling of the novel Pcs to nanoparticles was through covalent bonding and ligand exchange. These conjugates were supported onto electrospun polystyrene fibers and chitosan microbeads for use as photocatalysts. The efficiency of the immobilized Pcs and Pc-nanoparticles was assessed by the phototrasfromation of organic pollutants, methyl orange and Rhodamine 6G as model dyes. Upon conjugating phthalocyanines to nanoparticles, there was a great increase in the rate of photodegradation of the model dyes. The photodynamic activity of the novel phthalocyanines upon conjugating to nanoparticles and selected targeting agents is also reported. The targeting agents employed in this study are folic acid and polylysine. Conjugating the phthalocyanines to folic acid or polylysine improved the solubility of the phthalocyanines in aqueous media. The potency of the conjugates was investigated on breast (MCF-7), prostate and melanoma cancer cell lines. The phthalocyanines showed no toxicity in the absence of light. However, upon illumination, a concentration dependent cellular decrease was observed.
- Full Text:
- Date Issued: 2015
- Authors: Khoza, Phindile Brenda
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Photochemotherapy , Cancer -- Chemotherapy , Zinc oxide , Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4538 , http://hdl.handle.net/10962/d1017918
- Description: The synthesis and extensive spectroscopical characterization of novel phthalocyanines are reported. The new compounds were characterized by elemental analysis, FT-IR, ¹HNMR, mass spectrometry and UV–Vis spectroscopy. The new phthalocyanines showed remarkable photophysicochemical behaviour. The novel phthalocyanines were then conjugated to nanoparticles, silver and ZnO. The coupling of the novel Pcs to nanoparticles was through covalent bonding and ligand exchange. These conjugates were supported onto electrospun polystyrene fibers and chitosan microbeads for use as photocatalysts. The efficiency of the immobilized Pcs and Pc-nanoparticles was assessed by the phototrasfromation of organic pollutants, methyl orange and Rhodamine 6G as model dyes. Upon conjugating phthalocyanines to nanoparticles, there was a great increase in the rate of photodegradation of the model dyes. The photodynamic activity of the novel phthalocyanines upon conjugating to nanoparticles and selected targeting agents is also reported. The targeting agents employed in this study are folic acid and polylysine. Conjugating the phthalocyanines to folic acid or polylysine improved the solubility of the phthalocyanines in aqueous media. The potency of the conjugates was investigated on breast (MCF-7), prostate and melanoma cancer cell lines. The phthalocyanines showed no toxicity in the absence of light. However, upon illumination, a concentration dependent cellular decrease was observed.
- Full Text:
- Date Issued: 2015
The development of biological tools to aid in the genetic investigation of the black (Diceros bicornis) and white (Ceratotherium simum) rhinoceros mitochondrial genomes
- Authors: Parsons, Michelle
- Date: 2015
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/56059 , vital:26769
- Description: The black (Diceros bicornis) and white (Ceratotherium simum) rhinoceros are found in South Africa. A decline in the populations of these species has resulted due to human activities such as habitat fragmentation and poaching. This has contributed to the loss of genetic diversity amongst the black and white rhinoceros. Conservation and anti-poaching efforts are needed to help maintain genetic diversity. These efforts could be improved through the development of non-invasive techniques to examine DNA from threatened animals. The aim of this research was to develop a molecular technique which would allow for the identification of the black and white rhinoceros and to develop a molecular technique which would allow for intraspecies genetic variation to be examined. DNA extractions were performed on matched faecal and tissue samples that were collected from two regions in South Africa. Polymerase chain reaction (PCR) primer sets were designed to investigate several regions of the rhinoceros mitochondrial genome. PCR optimisation was completed for the target regions. Sequencing was conducted on all final PCR products. The cytochrome c oxidase subunit 1 (COIi) gene allowed for the rhinoceros family to be identified. This region was digested with the HindIII restriction enzyme, which allowed for the specific identification of either the black or white rhinoceros. A subsequent region of the cytochrome c oxidase subunit 1 (COIii) as well as the D-loop, hypervariable regions (HV1 and HV2), cytochrome b (cytb) and 16s rRNA regions were investigated. These regions displayed potential for establishing geographic origin for black rhinoceros samples, whereas the D-loop and HV2 show potential for the white rhinoceros. The white rhinoceros displayed sequence variation in the HV2 and cytb region, while variation was observed in the COIi and HV1 for the black rhinoceros. All investigated target regions allowed for the rhinoceros family to be identified. The COI (COIi and COIii), HV2 and cytb regions allowed for the subspecies of rhinoceros to be identified, however the D-loop was not able to identify the white rhinoceros species. The 16s rRNA and HV1 regions allowed for the correct subspecies of rhinoceros to be identified, however as the primers were only compatible for the black rhinoceros therefore a subsequent investigation is required for the white rhinoceros. The establishment of this novel PCR based technique to identify white and black rhinoceros will allow for efficient species identification in wildlife forensic cases. A biological method was established to study intraspecies variation for the white and black rhinoceros; however the investigated target regions did not yield sufficient genetic variation. The core techniques developed in this study will be valuable for future studies that wish to investigate genetic variation in mammal species.
- Full Text:
- Date Issued: 2015
- Authors: Parsons, Michelle
- Date: 2015
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/56059 , vital:26769
- Description: The black (Diceros bicornis) and white (Ceratotherium simum) rhinoceros are found in South Africa. A decline in the populations of these species has resulted due to human activities such as habitat fragmentation and poaching. This has contributed to the loss of genetic diversity amongst the black and white rhinoceros. Conservation and anti-poaching efforts are needed to help maintain genetic diversity. These efforts could be improved through the development of non-invasive techniques to examine DNA from threatened animals. The aim of this research was to develop a molecular technique which would allow for the identification of the black and white rhinoceros and to develop a molecular technique which would allow for intraspecies genetic variation to be examined. DNA extractions were performed on matched faecal and tissue samples that were collected from two regions in South Africa. Polymerase chain reaction (PCR) primer sets were designed to investigate several regions of the rhinoceros mitochondrial genome. PCR optimisation was completed for the target regions. Sequencing was conducted on all final PCR products. The cytochrome c oxidase subunit 1 (COIi) gene allowed for the rhinoceros family to be identified. This region was digested with the HindIII restriction enzyme, which allowed for the specific identification of either the black or white rhinoceros. A subsequent region of the cytochrome c oxidase subunit 1 (COIii) as well as the D-loop, hypervariable regions (HV1 and HV2), cytochrome b (cytb) and 16s rRNA regions were investigated. These regions displayed potential for establishing geographic origin for black rhinoceros samples, whereas the D-loop and HV2 show potential for the white rhinoceros. The white rhinoceros displayed sequence variation in the HV2 and cytb region, while variation was observed in the COIi and HV1 for the black rhinoceros. All investigated target regions allowed for the rhinoceros family to be identified. The COI (COIi and COIii), HV2 and cytb regions allowed for the subspecies of rhinoceros to be identified, however the D-loop was not able to identify the white rhinoceros species. The 16s rRNA and HV1 regions allowed for the correct subspecies of rhinoceros to be identified, however as the primers were only compatible for the black rhinoceros therefore a subsequent investigation is required for the white rhinoceros. The establishment of this novel PCR based technique to identify white and black rhinoceros will allow for efficient species identification in wildlife forensic cases. A biological method was established to study intraspecies variation for the white and black rhinoceros; however the investigated target regions did not yield sufficient genetic variation. The core techniques developed in this study will be valuable for future studies that wish to investigate genetic variation in mammal species.
- Full Text:
- Date Issued: 2015
The relationship between organisational commitment, work engagement and turnover intentions
- Authors: Robinson, Nicole Dianne
- Date: 2015
- Subjects: Social responsibility of business , Organizational commitment , Labor turnover
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10948/6582 , vital:21119
- Description: “The question of employee turnover has come to gain greater attention especially in the 21st century where organisations all over the world, in various industries, have faced this problem at some stages of their evolution” (Zahra et al, 2013:78). Turnover intentions have further become a vital study for organisations and researchers as research has found that once an employee has actually implemented the behaviour to quit, it is highly unlikely that an employer will be able to “gain access to them to understand their prior situation” (Darroux, Johnathan & Thibeli, 2013:78). Several studies have been devoted to examine the impact of various factors such as organisational commitment, work engagement, age, gender and tenure on turnover intentions in an attempt to assist organisations in alleviating the challenges associated with turnover (Darroux, Johnathan & Thibeli, 2013). The results of these studies have continually shown that both work engagement and organisational commitment have a significant effect on turnover intentions (Yin & Yang, 2002; Meyer, Stanley, Herscovitch & Topolnytsky, 2002 and Tett & Meyer, 1993).
- Full Text:
- Date Issued: 2015
- Authors: Robinson, Nicole Dianne
- Date: 2015
- Subjects: Social responsibility of business , Organizational commitment , Labor turnover
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10948/6582 , vital:21119
- Description: “The question of employee turnover has come to gain greater attention especially in the 21st century where organisations all over the world, in various industries, have faced this problem at some stages of their evolution” (Zahra et al, 2013:78). Turnover intentions have further become a vital study for organisations and researchers as research has found that once an employee has actually implemented the behaviour to quit, it is highly unlikely that an employer will be able to “gain access to them to understand their prior situation” (Darroux, Johnathan & Thibeli, 2013:78). Several studies have been devoted to examine the impact of various factors such as organisational commitment, work engagement, age, gender and tenure on turnover intentions in an attempt to assist organisations in alleviating the challenges associated with turnover (Darroux, Johnathan & Thibeli, 2013). The results of these studies have continually shown that both work engagement and organisational commitment have a significant effect on turnover intentions (Yin & Yang, 2002; Meyer, Stanley, Herscovitch & Topolnytsky, 2002 and Tett & Meyer, 1993).
- Full Text:
- Date Issued: 2015
A study of the identification and awareness level of students towards the Eastcape Midlands FET college brand
- Authors: Pienaar, Alicia Nicole
- Date: 2015
- Subjects: Branding (Marketing) -- South Africa , Education, Higher -- South Africa Corporate culture -- South Africa
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10948/3125 , vital:20401
- Description: Since 1994, South Africa has been revamping its higher education system as part of a broader national reform movement aimed at overcoming the inequities and divisions caused by the now obsolete apartheid regime (Sedgwick, 2004). This treatise firstly describes and then explores if students identify themselves with the EMC corporate identity. Thereafter, it firstly explores and then describes the corporate identity awareness level of EMC students. An exploratory-descriptive research design was used. The researcher used two types of data. One was secondary data and the other one was primary data. The former were collected by means of an extensive review of the related literature. The latter were obtained by means of online questionnaires. The level of brand awareness among students is considered to be low. There is a need to improve the corporate identity awareness level of these strategic stakeholders for the future success of the college. This treatise concentrated on the parent brand (EMC). Furthermore, the sampling has been limited to students studying at EMC (Uitenhage campuses). It is important to explore the corporate brand awareness level of the students. It is also essential to discover if students identify themselves with the EMC brand.
- Full Text:
- Date Issued: 2015
- Authors: Pienaar, Alicia Nicole
- Date: 2015
- Subjects: Branding (Marketing) -- South Africa , Education, Higher -- South Africa Corporate culture -- South Africa
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10948/3125 , vital:20401
- Description: Since 1994, South Africa has been revamping its higher education system as part of a broader national reform movement aimed at overcoming the inequities and divisions caused by the now obsolete apartheid regime (Sedgwick, 2004). This treatise firstly describes and then explores if students identify themselves with the EMC corporate identity. Thereafter, it firstly explores and then describes the corporate identity awareness level of EMC students. An exploratory-descriptive research design was used. The researcher used two types of data. One was secondary data and the other one was primary data. The former were collected by means of an extensive review of the related literature. The latter were obtained by means of online questionnaires. The level of brand awareness among students is considered to be low. There is a need to improve the corporate identity awareness level of these strategic stakeholders for the future success of the college. This treatise concentrated on the parent brand (EMC). Furthermore, the sampling has been limited to students studying at EMC (Uitenhage campuses). It is important to explore the corporate brand awareness level of the students. It is also essential to discover if students identify themselves with the EMC brand.
- Full Text:
- Date Issued: 2015
Nonlinear optical studies of phthalocyanines and their conjugates with nanomaterials
- Authors: Sanusi, Sikiru Olukayode
- Date: 2015
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4545 , http://hdl.handle.net/10962/d1017925
- Description: A number of metallophthalocyanines (MPcs) and metal-free phthalocyanines (H₂Pcs) have been synthesized and characterized using various characterization tools such as ¹H-NMR, TOF mass spectrometry, FT-IR, UV-visible spectrophotometry and CHNS elemental analysis. Some of the MPcs were covalently linked to nanomaterials such as silica nanoparticles (SiNPs), single-walled carbon nanotubes (SWCNTs), magnetite nanoparticles (MNPs) and quantum dots (QDs), or embedded in polymer thin-films using poly(methyl methacrylate) (PMMA) and poly(acrylic acid) (PAA) as the polymer sources. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), thermogravimetry analysis and X-ray diffractometry. The nonlinear optical (NLO) properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. In general, most of the investigated MPcs showed good optical limiting behaviors, except for a few, like the non-peripherally-substituted 2-pyridyloxy phthalocyanines, which showed inhibited NLO response as a result of the ring-strain effects. The absence of a metal center was found to greatly reduce the inherent high nonlinearities expected of some of the phthalocyanine complexes. The octaphenoxy derivatives (61a – 61e) were found to exhibit reverse saturable absorption (RSA) that depends on the singlet-singlet transitions, hence making them less reliable optical limiters. The optical limiting properties of the MPcs were improved in the presence of nanomaterials such as the QDs, MNPs and SWCNTs, with MPc-QDs showing the best optical limiting behavior of the three. SiNPs have no significant effect on the optical limiting behavior of the MPcs. The optical limiting properties of the MPcs were greatly enhanced in the presence of PMMA or PAA polymers. The PAA polymer showed better optical limiting behavior compared to PMMA
- Full Text:
- Date Issued: 2015
- Authors: Sanusi, Sikiru Olukayode
- Date: 2015
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4545 , http://hdl.handle.net/10962/d1017925
- Description: A number of metallophthalocyanines (MPcs) and metal-free phthalocyanines (H₂Pcs) have been synthesized and characterized using various characterization tools such as ¹H-NMR, TOF mass spectrometry, FT-IR, UV-visible spectrophotometry and CHNS elemental analysis. Some of the MPcs were covalently linked to nanomaterials such as silica nanoparticles (SiNPs), single-walled carbon nanotubes (SWCNTs), magnetite nanoparticles (MNPs) and quantum dots (QDs), or embedded in polymer thin-films using poly(methyl methacrylate) (PMMA) and poly(acrylic acid) (PAA) as the polymer sources. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), thermogravimetry analysis and X-ray diffractometry. The nonlinear optical (NLO) properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. In general, most of the investigated MPcs showed good optical limiting behaviors, except for a few, like the non-peripherally-substituted 2-pyridyloxy phthalocyanines, which showed inhibited NLO response as a result of the ring-strain effects. The absence of a metal center was found to greatly reduce the inherent high nonlinearities expected of some of the phthalocyanine complexes. The octaphenoxy derivatives (61a – 61e) were found to exhibit reverse saturable absorption (RSA) that depends on the singlet-singlet transitions, hence making them less reliable optical limiters. The optical limiting properties of the MPcs were improved in the presence of nanomaterials such as the QDs, MNPs and SWCNTs, with MPc-QDs showing the best optical limiting behavior of the three. SiNPs have no significant effect on the optical limiting behavior of the MPcs. The optical limiting properties of the MPcs were greatly enhanced in the presence of PMMA or PAA polymers. The PAA polymer showed better optical limiting behavior compared to PMMA
- Full Text:
- Date Issued: 2015
The trophic ecology of the endangered endemic Barau's Petrel (Pterodroma baraui) from Reunion Island, south-western Indian Ocean
- Authors: Danckwerts, Daniel Keith
- Date: 2015
- Subjects: Petrels -- Réunion , Pterodroma baraui , Ecology -- Réunion
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5925 , http://hdl.handle.net/10962/d1017803
- Description: Réunion is the only tropical island that supports two endemic gadfly petrels. Population modelling has indicated that the current threats to the Barau’s Petrel (Pterodroma baraui) may drive it to extinction; this fate is almost definite for the Mascarene Petrel (Pseudobulweria aterrima). Management interventions have therefore been implemented, but conservation potential is handicapped since virtually nothing is known about the former species’ at-sea biology. Thus, following numerous recommendations, this study aimed to combine stomach content, stable isotope, and fatty acid analyses so to provide new information on the at-sea ecology of Barau’s Petrel. Breeding colonies were repeatedly visited over the same season and samples gathered from adults, fledglings, and downy chicks. Stomach contents consisted mostly of accumulated cephalopod beaks whereas structures from fishes, molluscs, arthropods, and crustaceans were less frequently encountered. Fatty acid profiles of blood varied greatly among individuals and the lowincidences of monounsaturated and n-3 fatty acids discounted fish as an important dietary component. δ¹⁵N of blood indicated a niche between the fourth and fifth trophic levels, which proposes that these birds scavenge to a greater degree than other sympatric seabirds and suggests that adults are also reliant on their endogenous reserves during breeding. δ¹³C values confirmed the migratory behaviour of adults since birds returning from the non-breeding grounds were enriched relative to individuals sampled through the breeding period. Significant intra-breeding season variations in δ13C were also observed, which matched this species’ patterns of habitat use as have recently described. These results collectively indicate an opportunistic behaviour, which implies some degree of resilience against shifts in prey availability/accessibility, and suggest that this species’ reproduction isdependent on distant foraging areas. This breeding strategy is synonymous with great vulnerability as over-investing into a single breeding episode may jeopardize future survival and fecundity. Thus, in light of environmental conditions that are becoming increasingly more susceptible to dramatic changes, the birds could rather be prioritising adult survival, over reproductive output. Further work is obviously necessary and should benefit from databases of fatty acid profiles and isotope signatures of potential prey species.
- Full Text:
- Date Issued: 2015
- Authors: Danckwerts, Daniel Keith
- Date: 2015
- Subjects: Petrels -- Réunion , Pterodroma baraui , Ecology -- Réunion
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5925 , http://hdl.handle.net/10962/d1017803
- Description: Réunion is the only tropical island that supports two endemic gadfly petrels. Population modelling has indicated that the current threats to the Barau’s Petrel (Pterodroma baraui) may drive it to extinction; this fate is almost definite for the Mascarene Petrel (Pseudobulweria aterrima). Management interventions have therefore been implemented, but conservation potential is handicapped since virtually nothing is known about the former species’ at-sea biology. Thus, following numerous recommendations, this study aimed to combine stomach content, stable isotope, and fatty acid analyses so to provide new information on the at-sea ecology of Barau’s Petrel. Breeding colonies were repeatedly visited over the same season and samples gathered from adults, fledglings, and downy chicks. Stomach contents consisted mostly of accumulated cephalopod beaks whereas structures from fishes, molluscs, arthropods, and crustaceans were less frequently encountered. Fatty acid profiles of blood varied greatly among individuals and the lowincidences of monounsaturated and n-3 fatty acids discounted fish as an important dietary component. δ¹⁵N of blood indicated a niche between the fourth and fifth trophic levels, which proposes that these birds scavenge to a greater degree than other sympatric seabirds and suggests that adults are also reliant on their endogenous reserves during breeding. δ¹³C values confirmed the migratory behaviour of adults since birds returning from the non-breeding grounds were enriched relative to individuals sampled through the breeding period. Significant intra-breeding season variations in δ13C were also observed, which matched this species’ patterns of habitat use as have recently described. These results collectively indicate an opportunistic behaviour, which implies some degree of resilience against shifts in prey availability/accessibility, and suggest that this species’ reproduction isdependent on distant foraging areas. This breeding strategy is synonymous with great vulnerability as over-investing into a single breeding episode may jeopardize future survival and fecundity. Thus, in light of environmental conditions that are becoming increasingly more susceptible to dramatic changes, the birds could rather be prioritising adult survival, over reproductive output. Further work is obviously necessary and should benefit from databases of fatty acid profiles and isotope signatures of potential prey species.
- Full Text:
- Date Issued: 2015
Photophysicochemical properties and in vitro photodynamic therapy activities of zinc phthalocyanine conjugates with biomolecules and single-walled carbon nanotubes
- Authors: Ogbodu, Racheal O
- Date: 2015
- Subjects: Photochemotherapy , Phthalocyanines , Biomolecules
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4544 , http://hdl.handle.net/10962/d1017924
- Description: The synthesis, photophysicochemcial properties, in vitro dark toxicity and photodynamic therapy (PDT) activities of different derivatives of zinc phthalocyanine (ZnPc) conjugates with biomolecules (folic acid, bovine serum albumin (BSA), ascorbic acid, uridine or spermine) and single-walled carbon nanotubes (SWCNTs) are presented in this work. The fluorescence quantum yields (ΦF) (Subscript F) of the ZnPc derivatives or ZnPc-biomolecule conjugates remained relatively the same as compared to the precursor Pcs. Slight increases were observed in the ΦF (Subscript F) values of conjugates containing substituents such as pyrene, folic acid or BSA with intrinsic fluorescence properties. The triplet quantum yield (ΦT ) (Subscript T) values for some ZnPc conjugates increases compared to the precursor ZnPcs due to extended π conjugation (for the conjugate with pyrene) and the presence of phenyl ring that support spin-orbit charge transfer intersystem crossing to triplet state. While some conjugates showed decreases in the ΦT (Subscript T) values compared to precursor ZnPcs due to the presence of substituents that could quench photo-excited state properties. The singlet oxygen quantum yield (ΦΔ ) values follow the trends of the triplet quantum yield values. The conjugates containing BSA also show increases in the ΦΔ values without corresponding increases in ΦT (Subscript T) values due to the ability of BSA to generate free radicals including singlet oxygen. The presence of SWCNTs decreases the photophysicochemcial properties of some ZnPc-SWCNT conjugates compared to the precursor ZnPcs due to photo-induced electron transfer from an excited Pc complex (electron donor) to SWCNTs (electron acceptor). However, increases were observed in some ZnPc-SWCNT conjugates as a result of fast charge recombination process due to highly short-lived radical ion pair produced. These phenomena affected the ΦF (Suscript F) values, ΦT (Suscript T) values, and the ΦΔ values. Increases or decreases in ΦT (Suscript T) values resulted in corresponding increases or decreases in ΦΔ values
- Full Text:
- Date Issued: 2015
- Authors: Ogbodu, Racheal O
- Date: 2015
- Subjects: Photochemotherapy , Phthalocyanines , Biomolecules
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4544 , http://hdl.handle.net/10962/d1017924
- Description: The synthesis, photophysicochemcial properties, in vitro dark toxicity and photodynamic therapy (PDT) activities of different derivatives of zinc phthalocyanine (ZnPc) conjugates with biomolecules (folic acid, bovine serum albumin (BSA), ascorbic acid, uridine or spermine) and single-walled carbon nanotubes (SWCNTs) are presented in this work. The fluorescence quantum yields (ΦF) (Subscript F) of the ZnPc derivatives or ZnPc-biomolecule conjugates remained relatively the same as compared to the precursor Pcs. Slight increases were observed in the ΦF (Subscript F) values of conjugates containing substituents such as pyrene, folic acid or BSA with intrinsic fluorescence properties. The triplet quantum yield (ΦT ) (Subscript T) values for some ZnPc conjugates increases compared to the precursor ZnPcs due to extended π conjugation (for the conjugate with pyrene) and the presence of phenyl ring that support spin-orbit charge transfer intersystem crossing to triplet state. While some conjugates showed decreases in the ΦT (Subscript T) values compared to precursor ZnPcs due to the presence of substituents that could quench photo-excited state properties. The singlet oxygen quantum yield (ΦΔ ) values follow the trends of the triplet quantum yield values. The conjugates containing BSA also show increases in the ΦΔ values without corresponding increases in ΦT (Subscript T) values due to the ability of BSA to generate free radicals including singlet oxygen. The presence of SWCNTs decreases the photophysicochemcial properties of some ZnPc-SWCNT conjugates compared to the precursor ZnPcs due to photo-induced electron transfer from an excited Pc complex (electron donor) to SWCNTs (electron acceptor). However, increases were observed in some ZnPc-SWCNT conjugates as a result of fast charge recombination process due to highly short-lived radical ion pair produced. These phenomena affected the ΦF (Suscript F) values, ΦT (Suscript T) values, and the ΦΔ values. Increases or decreases in ΦT (Suscript T) values resulted in corresponding increases or decreases in ΦΔ values
- Full Text:
- Date Issued: 2015
Geological and geophysical investigation of the South Eastern Karoo Basin, South Africa
- Authors: Baiyegunhi, Christopher
- Date: 2015
- Language: English
- Type: Thesis , Masters , MSc (Geology)
- Identifier: vital:11532 , http://hdl.handle.net/10353/d1021280
- Description: Geological and geophysical methods were used to investigate the southeastern Karoo Basin of South Africa in an area extending from longitudes 24 o E to 29o E and latitudes 32o S to 35o S. This was undertaken in order to reveal geologic structures, isochore thicknesses of the geologic sequence and their variations across the study area, proffer the possible provenance of the sediments and assess the potential of oil and gas accumulation. The methodology used includes field investigation, rock sampling, preparation of thin sections, petrographic studies, X-ray diffraction analysis, density measurements, porosity calculations, extraction of elevation data from Google Earth, 2½ D gravity profile modelling, generating of isochore (true vertical) thicknesses and depositional surfaces maps from the models, PetroMod 1D modelling and qualitative interpretation of magnetic, gravity and radiometric maps.Petrographic study was carried out on twenty six thin sections of rocks from the eleven geologic formations that cover the study area. Petrographic studies on the diamictite of the Dwyka Group shows abundance of monocrystalline quartz, granite and quartzite components in the breccias which possibly indicate the existence of granitic and metamorphic rocks in the source areas. The sandstones of the Ecca and Beaufort Groups are immature, greywacke and the heavy mineral assemblages signify that the minerals are of granitic, volcanic and metamorphic origin. The magnetic maps show two main magnetic anomalies, a major one trending in a northeast to southwest direction which is part of the Beattie magnetic anomaly and another that is a “bean-shaped” anomaly. The radially averaged power spectrum shows two depths to magnetic sources. The first depth is about 0.6 km which is the average depth to the top of the shallow sources, while the average depth to the top of the deep sources is about 15 km. The shallow sources are connected to magnetic minerals within the Beaufort Group while deep magnetic sources were inferred to be in the basement. The gamma ray spectrometric map shows areas with relatively high gamma radiation count. The high radiation count is possibly due to the uranium and thorium in the detrital materials, as well as the enrichment of radioelements in the feldspars (k-feldspar), calcite, quartz, zircon and clay minerals in the fluvial channel sandstones of the Beaufort Group. A total of two hundred and fifty-eight (258) rock samples were collected in the field and densities (dry, wet and grain densities) and porosities were determined in the laboratory. The Karoo Supergroup density values range from 2.526 – 2.828 g/cm3. The average porosities range from 0. 49 – 3.31 %. The dry densities and porosities of all the formations are inversely correlated with correlation coefficient values (R) that range from 0.9491 - 0.9982. The density of the dolerite intrusions (mostly sill) ranges from 2.700 – 2.837 g/cm3 whilst the porosity range from 0.1118 – 0.3868 %. The Bouguer anomaly map shows an increase in gravity values from -140.7 mGal in inland to about 60.1 mGal in coastal areas. This dominant gravity variation is inferred to be due to a deeper basement and/or Moho that get shallower from inland towards the coast. The Moho is at about 45 km depth inland and shallows to about 42 km at the coast. The 2½ D gravity modelling was done for fourteen (14) profiles with each profile having three (3) models corresponding to minimum, average and maximum densities to obtain the thicknesses of the geologic sequence. The current isochore thicknesses extracted from the gravity models show that the Beaufort Group is the thickest of all the groups that make up the Karoo Supergroup with maximum vertical thickness of up to 634 m, followed by the Ecca and Dwyka Groups with maximum vertical thicknesses of about 3207 m and 727 m, respectively. The maximum elevation for the Dwyka, Ecca and Beaufort sediments are about 500 m, 400 m and 285 m, respectively, whilst the maximum depth below sea level are around 8500 m, 7000 m and 5500 m, respectively. The PetroMod1D model result yield average vitrinite reflectance and temperature values of about 6 % and 500 ℃ respectively for the lower Ecca Group which belong to the dry gas window based on classification by several authors. Thus the rocks of the lower Ecca Group are thermally matured for hydrocarbon (shale gas) generation that can merit gas exploration in the Karoo Basin.
- Full Text:
- Date Issued: 2015
- Authors: Baiyegunhi, Christopher
- Date: 2015
- Language: English
- Type: Thesis , Masters , MSc (Geology)
- Identifier: vital:11532 , http://hdl.handle.net/10353/d1021280
- Description: Geological and geophysical methods were used to investigate the southeastern Karoo Basin of South Africa in an area extending from longitudes 24 o E to 29o E and latitudes 32o S to 35o S. This was undertaken in order to reveal geologic structures, isochore thicknesses of the geologic sequence and their variations across the study area, proffer the possible provenance of the sediments and assess the potential of oil and gas accumulation. The methodology used includes field investigation, rock sampling, preparation of thin sections, petrographic studies, X-ray diffraction analysis, density measurements, porosity calculations, extraction of elevation data from Google Earth, 2½ D gravity profile modelling, generating of isochore (true vertical) thicknesses and depositional surfaces maps from the models, PetroMod 1D modelling and qualitative interpretation of magnetic, gravity and radiometric maps.Petrographic study was carried out on twenty six thin sections of rocks from the eleven geologic formations that cover the study area. Petrographic studies on the diamictite of the Dwyka Group shows abundance of monocrystalline quartz, granite and quartzite components in the breccias which possibly indicate the existence of granitic and metamorphic rocks in the source areas. The sandstones of the Ecca and Beaufort Groups are immature, greywacke and the heavy mineral assemblages signify that the minerals are of granitic, volcanic and metamorphic origin. The magnetic maps show two main magnetic anomalies, a major one trending in a northeast to southwest direction which is part of the Beattie magnetic anomaly and another that is a “bean-shaped” anomaly. The radially averaged power spectrum shows two depths to magnetic sources. The first depth is about 0.6 km which is the average depth to the top of the shallow sources, while the average depth to the top of the deep sources is about 15 km. The shallow sources are connected to magnetic minerals within the Beaufort Group while deep magnetic sources were inferred to be in the basement. The gamma ray spectrometric map shows areas with relatively high gamma radiation count. The high radiation count is possibly due to the uranium and thorium in the detrital materials, as well as the enrichment of radioelements in the feldspars (k-feldspar), calcite, quartz, zircon and clay minerals in the fluvial channel sandstones of the Beaufort Group. A total of two hundred and fifty-eight (258) rock samples were collected in the field and densities (dry, wet and grain densities) and porosities were determined in the laboratory. The Karoo Supergroup density values range from 2.526 – 2.828 g/cm3. The average porosities range from 0. 49 – 3.31 %. The dry densities and porosities of all the formations are inversely correlated with correlation coefficient values (R) that range from 0.9491 - 0.9982. The density of the dolerite intrusions (mostly sill) ranges from 2.700 – 2.837 g/cm3 whilst the porosity range from 0.1118 – 0.3868 %. The Bouguer anomaly map shows an increase in gravity values from -140.7 mGal in inland to about 60.1 mGal in coastal areas. This dominant gravity variation is inferred to be due to a deeper basement and/or Moho that get shallower from inland towards the coast. The Moho is at about 45 km depth inland and shallows to about 42 km at the coast. The 2½ D gravity modelling was done for fourteen (14) profiles with each profile having three (3) models corresponding to minimum, average and maximum densities to obtain the thicknesses of the geologic sequence. The current isochore thicknesses extracted from the gravity models show that the Beaufort Group is the thickest of all the groups that make up the Karoo Supergroup with maximum vertical thickness of up to 634 m, followed by the Ecca and Dwyka Groups with maximum vertical thicknesses of about 3207 m and 727 m, respectively. The maximum elevation for the Dwyka, Ecca and Beaufort sediments are about 500 m, 400 m and 285 m, respectively, whilst the maximum depth below sea level are around 8500 m, 7000 m and 5500 m, respectively. The PetroMod1D model result yield average vitrinite reflectance and temperature values of about 6 % and 500 ℃ respectively for the lower Ecca Group which belong to the dry gas window based on classification by several authors. Thus the rocks of the lower Ecca Group are thermally matured for hydrocarbon (shale gas) generation that can merit gas exploration in the Karoo Basin.
- Full Text:
- Date Issued: 2015
Characterisation of performance limiting defects in photovoltaic devices using electroluminescence and related techniques
- Authors: Crozier, Jacqueline Louise
- Date: 2015
- Subjects: Photovoltaic cells Solar cells Photovoltaic power systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11004 , vital:26866
- Description: Solar cells allow the energy from the sun to be converted into electrical energy; this makes solar energy an environmentally friendly, sustainable alternative to fossil fuel energy sources. Solar cells are connected together in a photovoltaic (PV) module to provide the higher current, voltage and power outputs necessary for electrical applications. However, the performance of PV modules can limited by the degradation and defects. PV modules can be characterised using various opto-electronic techniques, each providing information about the performance of the module. The current-voltage (I-V) characteristic curve of a module being the most commonly used characterisation technique. The I-V curve is typically measured in outdoor, fully illuminated, conditions. This allows performance parameters such as short circuit current (ISC), open circuit voltage (VOC) and maximum power (PMAX) to be determined. However, it can be difficult to determine the root cause of the performance drop from the I-V curve alone. Electroluminescence (EL) is a module characterisation technique that allows defects and failures in PV modules to be successfully identified. This study investigates the characterisation of solar cells and photovoltaic modules using EL. EL occurs when a solar cell or module is forward biased and the injected electron-hole pairs recombine radiatively. The intensity of the emitted EL is related the applied voltage and the material properties. EL imaging is a useful characterisation technique in identifying module defects and failures. Defects such as micro-cracks, broken contact fingers and fractures are detected in EL images as well as material features such as grain boundaries. The common defects in crystalline silicon are catalogued and the possible causes are discussed. An experimental setup was developed in order to systematically take a high resolution EL image of every cell in the module and record the applied voltage and current. This produces a very detailed, clear, image of each cell with a pixel size in the micrometre range. This process is time consuming to acquire an EL image of an entire module so alternatively a different setup can be used and an EL image of a whole module can be captured in a single frame with an increased pixel size in the millimetre range. For EL imaging a silicon charge-coupled device (CCD) camera was used because it has very good spatial resolution however this sensor is only sensitive to wavelength in the range of 300-1200 nm. There is an overlap in wavelengths from about 900 to 1100 nm allowing the EL emitted from silicon solar cells to be detected. In conjunction with the high-resolution EL system an image processing program was developed to crop, adjust and align the images so only the relevant cell was included. This program also automatically detects certain defects that have a regular shape. Micro-cracks, broken fingers and striation rings are automatically identified. The program has an adjustable sensitivity to identify small or large defects. Defective cells are distinguished from undamaged cells by comparing the binary images to the ideal, undamaged cell. The current-voltage curves and the performance parameters of modules were compared with the EL images in order to discuss and identify power limiting defects. Features that remove significant portions of the cell from electrical contact such as micro-cracks are shown to have a larger effect of the performance of the module. Other features such as broken contact fingers, contact forming failures and striation rings do not significantly lower the performance of the module. Thus an understanding of how different features affect the module performance is important in order to correctly interpret the EL results. The intensity of the luminescence emitted is related to the applied voltage and the quantum efficiency of the cell material. The spectrum of the emitted luminescence was modelled and related to the recombination properties of the cell such as surface recombination velocity and minority carrier diffusion length/lifetime. In this study the emitted spectrum was modelled and the effects of recombination properties of the cell on the emitted spectrum were examined. The spectrum of the detected EL was modelled, dependent on the sensitivity of the camera, the transmission of the filters and the emitted photon flux. The integration of short-pass filters into the experimental setup in order to isolate short-wavelength luminescence was discussed. There is a proportional relationship between the intensity of the emitted EL and the local junction voltage. Resistive losses like series and shunt resistances lower the applied voltage and thus affect the EL image. The voltage dependence was assessed by comparing EL images taken at different applied biases. Analysis of the variation in EL intensity with voltage was successful in determining the origin of certain features in an EL image. Certain defects, those that are related to series resistance or shunting are highly voltage dependent. When a feature has little or no dependence on voltage then the defect could be in the laminate layers and not in the cell material. The results of this study allow for in-depth analysis of the defects found in PV modules using the high resolution EL imaging system and the image processing routine. The development of an image processing routine allows the interpretation of the EL image to be done automatically, resulting in a faster and more efficient process. By understanding the defects visible in the EL image, the test is more meaningful and allows the results to be used to predict module performance and potential failures.
- Full Text:
- Date Issued: 2015
- Authors: Crozier, Jacqueline Louise
- Date: 2015
- Subjects: Photovoltaic cells Solar cells Photovoltaic power systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11004 , vital:26866
- Description: Solar cells allow the energy from the sun to be converted into electrical energy; this makes solar energy an environmentally friendly, sustainable alternative to fossil fuel energy sources. Solar cells are connected together in a photovoltaic (PV) module to provide the higher current, voltage and power outputs necessary for electrical applications. However, the performance of PV modules can limited by the degradation and defects. PV modules can be characterised using various opto-electronic techniques, each providing information about the performance of the module. The current-voltage (I-V) characteristic curve of a module being the most commonly used characterisation technique. The I-V curve is typically measured in outdoor, fully illuminated, conditions. This allows performance parameters such as short circuit current (ISC), open circuit voltage (VOC) and maximum power (PMAX) to be determined. However, it can be difficult to determine the root cause of the performance drop from the I-V curve alone. Electroluminescence (EL) is a module characterisation technique that allows defects and failures in PV modules to be successfully identified. This study investigates the characterisation of solar cells and photovoltaic modules using EL. EL occurs when a solar cell or module is forward biased and the injected electron-hole pairs recombine radiatively. The intensity of the emitted EL is related the applied voltage and the material properties. EL imaging is a useful characterisation technique in identifying module defects and failures. Defects such as micro-cracks, broken contact fingers and fractures are detected in EL images as well as material features such as grain boundaries. The common defects in crystalline silicon are catalogued and the possible causes are discussed. An experimental setup was developed in order to systematically take a high resolution EL image of every cell in the module and record the applied voltage and current. This produces a very detailed, clear, image of each cell with a pixel size in the micrometre range. This process is time consuming to acquire an EL image of an entire module so alternatively a different setup can be used and an EL image of a whole module can be captured in a single frame with an increased pixel size in the millimetre range. For EL imaging a silicon charge-coupled device (CCD) camera was used because it has very good spatial resolution however this sensor is only sensitive to wavelength in the range of 300-1200 nm. There is an overlap in wavelengths from about 900 to 1100 nm allowing the EL emitted from silicon solar cells to be detected. In conjunction with the high-resolution EL system an image processing program was developed to crop, adjust and align the images so only the relevant cell was included. This program also automatically detects certain defects that have a regular shape. Micro-cracks, broken fingers and striation rings are automatically identified. The program has an adjustable sensitivity to identify small or large defects. Defective cells are distinguished from undamaged cells by comparing the binary images to the ideal, undamaged cell. The current-voltage curves and the performance parameters of modules were compared with the EL images in order to discuss and identify power limiting defects. Features that remove significant portions of the cell from electrical contact such as micro-cracks are shown to have a larger effect of the performance of the module. Other features such as broken contact fingers, contact forming failures and striation rings do not significantly lower the performance of the module. Thus an understanding of how different features affect the module performance is important in order to correctly interpret the EL results. The intensity of the luminescence emitted is related to the applied voltage and the quantum efficiency of the cell material. The spectrum of the emitted luminescence was modelled and related to the recombination properties of the cell such as surface recombination velocity and minority carrier diffusion length/lifetime. In this study the emitted spectrum was modelled and the effects of recombination properties of the cell on the emitted spectrum were examined. The spectrum of the detected EL was modelled, dependent on the sensitivity of the camera, the transmission of the filters and the emitted photon flux. The integration of short-pass filters into the experimental setup in order to isolate short-wavelength luminescence was discussed. There is a proportional relationship between the intensity of the emitted EL and the local junction voltage. Resistive losses like series and shunt resistances lower the applied voltage and thus affect the EL image. The voltage dependence was assessed by comparing EL images taken at different applied biases. Analysis of the variation in EL intensity with voltage was successful in determining the origin of certain features in an EL image. Certain defects, those that are related to series resistance or shunting are highly voltage dependent. When a feature has little or no dependence on voltage then the defect could be in the laminate layers and not in the cell material. The results of this study allow for in-depth analysis of the defects found in PV modules using the high resolution EL imaging system and the image processing routine. The development of an image processing routine allows the interpretation of the EL image to be done automatically, resulting in a faster and more efficient process. By understanding the defects visible in the EL image, the test is more meaningful and allows the results to be used to predict module performance and potential failures.
- Full Text:
- Date Issued: 2015
Assessment of water quality based on diatom indices in a small temperate river system, Kowie River, South Africa
- Dalu, Tatenda, Bere, Taurai, Froneman, P William
- Authors: Dalu, Tatenda , Bere, Taurai , Froneman, P William
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123896 , vital:35514 , http://dx.doi.org/10.4314/wsa.v42i2.02
- Description: This study aimed to assess the impact of land use patterns on water quality and benthic diatom community structure and to test the applicability of diatom indices developed in other regions of the world to a small temperate southern African river system. Sampling was conducted at eight study sites along the length of the river on four separate occasions. Multivariate data analyses were performed on the diatom community dataset to specify the main gradients of floristic variation and to detect and visualize similarities in diatom samples in relation to land-use patterns within the catchment. One hundred and twelve (112) diatom species belonging to 36 genera were recorded during the study. Canonical correspondence analysis (CCA) demonstrated that variations in the benthic diatom community structure were best explained by ammonium, nitrate, conductivity, pH, temperature, resistivity and water flow. OMNIDIA was used for calculation of selected diatom water quality indices. A number of the indices, e.g., the trophic diatom index (TDI), eutrophication/pollution index and biological index of water quality (BIWQ), either under- or over-estimated the water quality of the system. With few exceptions, there were no significant correlations (p> 0.05) between the diatom indices’ values and the nutrient variables. The absence of any significant correlations between the diatom indices’ values and selected physico-chemical variables suggests that indices developed in other regions of the world may not be suitable for temperate southern African rivers.
- Full Text:
- Date Issued: 2016
- Authors: Dalu, Tatenda , Bere, Taurai , Froneman, P William
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123896 , vital:35514 , http://dx.doi.org/10.4314/wsa.v42i2.02
- Description: This study aimed to assess the impact of land use patterns on water quality and benthic diatom community structure and to test the applicability of diatom indices developed in other regions of the world to a small temperate southern African river system. Sampling was conducted at eight study sites along the length of the river on four separate occasions. Multivariate data analyses were performed on the diatom community dataset to specify the main gradients of floristic variation and to detect and visualize similarities in diatom samples in relation to land-use patterns within the catchment. One hundred and twelve (112) diatom species belonging to 36 genera were recorded during the study. Canonical correspondence analysis (CCA) demonstrated that variations in the benthic diatom community structure were best explained by ammonium, nitrate, conductivity, pH, temperature, resistivity and water flow. OMNIDIA was used for calculation of selected diatom water quality indices. A number of the indices, e.g., the trophic diatom index (TDI), eutrophication/pollution index and biological index of water quality (BIWQ), either under- or over-estimated the water quality of the system. With few exceptions, there were no significant correlations (p> 0.05) between the diatom indices’ values and the nutrient variables. The absence of any significant correlations between the diatom indices’ values and selected physico-chemical variables suggests that indices developed in other regions of the world may not be suitable for temperate southern African rivers.
- Full Text:
- Date Issued: 2016