Movement patterns and habitat selection of invasive African sharptooth catfish
- Kadye, Wilbert T, Booth, Anthony J
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125276 , vital:35767 , http://dx.doi.10.1111/j.1469-7998.2012.00960.x
- Description: Information on the movement behaviour and habitat use by non-native invasive African catfish Clarias gariepinus is crucial in understanding and possibly mitigating its potential impacts. The aim of this study was to examine catfish movement and habitat selection within an invaded impoundment in the Eastern Cape, South Africa. Acoustic telemetry data for 10 tagged catfish were analyzed to identify spatial patterns in home ranges and seasonal changes in habitat associations. Long-distance movements were observed for most catfish from common central release point, whereas short-distance movements defined their home ranges and utilization distributions that were categorized as localized within single or multiple habitats. Habitat selection was non-random with most catfish utilizing the shallow river mouth and upper section of the reservoir that were dominated by a rocky substratum interspersed with submerged trees. These localities were likely to be preferred for spawning and/or feeding. Utilization of these habitats by catfish is likely to be associated with probable impact due to predation and interference competition for feeding and breeding grounds with other species. Although most catfish maintained their home ranges throughout the study, seasonal shifts in habitat use, which was reflected by the utilization of deep and silt-dominated habitats, were also observed for some catfish. Non-random habitat use and homing behaviour within single and multiple habitats by non-native sharptooth catfish suggests that its impact within the invaded habitats may be associated with particular habitats both at broad spatial and temporal scales. Protection of habitats from catfish invasion should be considered as a management option to conserve native biota.
- Full Text:
- Date Issued: 2013
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125276 , vital:35767 , http://dx.doi.10.1111/j.1469-7998.2012.00960.x
- Description: Information on the movement behaviour and habitat use by non-native invasive African catfish Clarias gariepinus is crucial in understanding and possibly mitigating its potential impacts. The aim of this study was to examine catfish movement and habitat selection within an invaded impoundment in the Eastern Cape, South Africa. Acoustic telemetry data for 10 tagged catfish were analyzed to identify spatial patterns in home ranges and seasonal changes in habitat associations. Long-distance movements were observed for most catfish from common central release point, whereas short-distance movements defined their home ranges and utilization distributions that were categorized as localized within single or multiple habitats. Habitat selection was non-random with most catfish utilizing the shallow river mouth and upper section of the reservoir that were dominated by a rocky substratum interspersed with submerged trees. These localities were likely to be preferred for spawning and/or feeding. Utilization of these habitats by catfish is likely to be associated with probable impact due to predation and interference competition for feeding and breeding grounds with other species. Although most catfish maintained their home ranges throughout the study, seasonal shifts in habitat use, which was reflected by the utilization of deep and silt-dominated habitats, were also observed for some catfish. Non-random habitat use and homing behaviour within single and multiple habitats by non-native sharptooth catfish suggests that its impact within the invaded habitats may be associated with particular habitats both at broad spatial and temporal scales. Protection of habitats from catfish invasion should be considered as a management option to conserve native biota.
- Full Text:
- Date Issued: 2013
An invader within an altered landscape: one catfish, two rivers and an inter-basin water transfer scheme
- Kadye, Wilbert T, Booth, Anthony J
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123776 , vital:35494 , https://doi.10.1002/rra.2599
- Description: African sharptooth catfish Clarias gariepinus has become established as a non-native invasive species in Eastern Cape, South Africa, where it was translocated primarily through an inter-basin water transfer scheme into the Great Fish and Sundays rivers. This study examined the patterns in catfish distribution and abundance, and compared trophic niches in relation to the ichthyofauna of the two rivers. Correspondence analysis revealed upstream to downstream gradients associated with the spatial distribution in species richness for most species within the mainstream and mainstream to tributary gradients that were associated mostly with the spatial distribution of native minnows in both rivers. Catfish was predicted to occur widely within the mainstream habitats and to decrease progressively from mainstreams to tributaries. Based on classification and regression trees, the physico-chemical environment was found to be a good proxy for predicting the occurrence and abundance of catfish. Although non-significant relationships were observed between catfish and other native fish species abundances, the study suggests potential impact due to predation and interference in habitats where the invader co-occurs with other fishes. Comparisons of trophic niches indicated higher trophic diversity for the mainstream ichthyofauna than the tributary communities in both rivers, suggesting an upstream to downstream continuum in community structure and resource availability. Catfish within the invaded mainstream had comparable trophic niches and similar dispersion patterns among individuals for both rivers, but indicated differences in shapes of scatter. This suggests that the catfish exhibited a differential response, probably in relation to resource availability, that may be indicative of its dietary plasticity. The study suggests the proliferation of catfish and its probable impact within the mainstream flow-altered habitats where invasion resistance was possibly reduced. Comparisons of trophic niches provided information on its probable impact at different scales and the potential risk of invasion of tributaries inhabited by native minnow species.
- Full Text:
- Date Issued: 2013
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123776 , vital:35494 , https://doi.10.1002/rra.2599
- Description: African sharptooth catfish Clarias gariepinus has become established as a non-native invasive species in Eastern Cape, South Africa, where it was translocated primarily through an inter-basin water transfer scheme into the Great Fish and Sundays rivers. This study examined the patterns in catfish distribution and abundance, and compared trophic niches in relation to the ichthyofauna of the two rivers. Correspondence analysis revealed upstream to downstream gradients associated with the spatial distribution in species richness for most species within the mainstream and mainstream to tributary gradients that were associated mostly with the spatial distribution of native minnows in both rivers. Catfish was predicted to occur widely within the mainstream habitats and to decrease progressively from mainstreams to tributaries. Based on classification and regression trees, the physico-chemical environment was found to be a good proxy for predicting the occurrence and abundance of catfish. Although non-significant relationships were observed between catfish and other native fish species abundances, the study suggests potential impact due to predation and interference in habitats where the invader co-occurs with other fishes. Comparisons of trophic niches indicated higher trophic diversity for the mainstream ichthyofauna than the tributary communities in both rivers, suggesting an upstream to downstream continuum in community structure and resource availability. Catfish within the invaded mainstream had comparable trophic niches and similar dispersion patterns among individuals for both rivers, but indicated differences in shapes of scatter. This suggests that the catfish exhibited a differential response, probably in relation to resource availability, that may be indicative of its dietary plasticity. The study suggests the proliferation of catfish and its probable impact within the mainstream flow-altered habitats where invasion resistance was possibly reduced. Comparisons of trophic niches provided information on its probable impact at different scales and the potential risk of invasion of tributaries inhabited by native minnow species.
- Full Text:
- Date Issued: 2013
Contributions of inshore and offshore sources of primary production to the foodweb, and the trophic connectivity between various habitats along a depth-gradient, in Sodwana Bay, Kwazulu-Natal, South Africa
- Authors: Parkinson, Matthew Cameron
- Date: 2013
- Subjects: Marine ecology -- South Africa -- Sodwana Bay , Food chains (Ecology) -- South Africa -- Sodwana Bay , Coastal ecology -- South Africa -- Sodwana Bay , Stable isotopes , Dinoflagellates , Marine algae
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5179 , http://hdl.handle.net/10962/d1001630 , Marine ecology -- South Africa -- Sodwana Bay , Food chains (Ecology) -- South Africa -- Sodwana Bay , Coastal ecology -- South Africa -- Sodwana Bay , Stable isotopes , Dinoflagellates , Marine algae
- Description: Sodwana Bay, situated within the iSimangaliso Wetland Park, is ecologically important as it contains high-latitude corals and the most southerly known population of coelacanths. This thesis utilised stable isotope and lipid analyses to investigate the trophic ecology of the area, in particular, understanding the relative contribution of inshore and offshore primary production to consumers inhabiting intertidal and shallow subtidal, coral reef, deep reef, canyon head and pelagic habitats. Seaweeds, excluding certain species of red seaweeds with highly depleted carbon signatures, and phytoplankton, such as diatoms, were found to be the principal sources of primary production for all consumers. Offshore production was typified by dinoflagellates. Particulate organic matter (POM) was spatio-temporally variable. Three distinct productivity periods related to nutrient cycling were noted with enriched carbon signatures and higher organic matter loads associated with warmer water. Inshore primary production was an important source of carbon to consumers in all habitats with the exception of zooplankton that were more reliant on pelagic primary production. Benthic invertebrates reflected a gradient in the utilisation of inshore production, due to the reduced availability of this source further offshore. Consumers at the furthest sites offshore were found to include a substantial quantity of inshore-derived production in their diets. Fishes, which are more mobile, were found to incorporate a similar proportion of inshore production into their diets regardless of where they were collected from.
- Full Text:
- Date Issued: 2013
- Authors: Parkinson, Matthew Cameron
- Date: 2013
- Subjects: Marine ecology -- South Africa -- Sodwana Bay , Food chains (Ecology) -- South Africa -- Sodwana Bay , Coastal ecology -- South Africa -- Sodwana Bay , Stable isotopes , Dinoflagellates , Marine algae
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5179 , http://hdl.handle.net/10962/d1001630 , Marine ecology -- South Africa -- Sodwana Bay , Food chains (Ecology) -- South Africa -- Sodwana Bay , Coastal ecology -- South Africa -- Sodwana Bay , Stable isotopes , Dinoflagellates , Marine algae
- Description: Sodwana Bay, situated within the iSimangaliso Wetland Park, is ecologically important as it contains high-latitude corals and the most southerly known population of coelacanths. This thesis utilised stable isotope and lipid analyses to investigate the trophic ecology of the area, in particular, understanding the relative contribution of inshore and offshore primary production to consumers inhabiting intertidal and shallow subtidal, coral reef, deep reef, canyon head and pelagic habitats. Seaweeds, excluding certain species of red seaweeds with highly depleted carbon signatures, and phytoplankton, such as diatoms, were found to be the principal sources of primary production for all consumers. Offshore production was typified by dinoflagellates. Particulate organic matter (POM) was spatio-temporally variable. Three distinct productivity periods related to nutrient cycling were noted with enriched carbon signatures and higher organic matter loads associated with warmer water. Inshore primary production was an important source of carbon to consumers in all habitats with the exception of zooplankton that were more reliant on pelagic primary production. Benthic invertebrates reflected a gradient in the utilisation of inshore production, due to the reduced availability of this source further offshore. Consumers at the furthest sites offshore were found to include a substantial quantity of inshore-derived production in their diets. Fishes, which are more mobile, were found to incorporate a similar proportion of inshore production into their diets regardless of where they were collected from.
- Full Text:
- Date Issued: 2013
Use of bioindicators and biomarkers to assess aquatic environmental contamination in selected urban wetlands in Uganda
- Authors: Naigaga, Irene
- Date: 2013
- Subjects: Indicators (Biology) Biochemical markers Environmental monitoring -- Uganda Water quality biological assessment -- Uganda Water -- Pollution -- Uganda Wetlands -- Monitoring -- Uganda Wetland management -- Uganda Aquatic resources -- Uganda Aquatic resources conservation -- Uganda Aquatic resources -- Management -- Uganda Fishes -- Histopathaology -- Uganda Urban ecology (Biology) -- Uganda
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5198 , http://hdl.handle.net/10962/d1002603
- Description: Pollution of aquatic resources in Uganda is on the increase and the trends are expected to increase with increase in population size and urbanisation. Assessment and mitigation of the environmental impacts on water quality and biodiversity have now become necessary. The aim of the study was to integrate invertebrate and fish as bioindicators and fish histopathology as a biomarker in the assessment of water quality deterioration in urban wetlands in Uganda. The integration harnesses the advantages and counteracts the shortcomings of each method and thus builds a more robust diagnostic tool that gives a better view of the impacts to the entire ecosystem. Four endpoints which included, physicochemical variables, benthic macroinvertebrate bioindicators, fish bioindicators and fish histopathology biomarkers were compared between varied effluent-impacted wetlands (Murchison Bay in Kampala, and Kirinya, Masese and Winday Bay in Jinja) and a non-impacted reference wetland (Lwanika in Mayuge). Results from the effluent-impacted sites differed from the less impacted reference site. The two sampling locations at Murchison Bay (inshore and offshore) and one sampling location at Kirinya (inshore), that were highly impacted with urban effluent, showed elevated nutrient levels, low pH, dissolved oxygen and secchi depth readings. This corresponded with low invertebrate taxa and fish species diversity and richness; and severe histopathological responses in liver, gonads and gills of O. niloticus. Sensitive taxa such as ephemeroptera and trichoptera were completely absent while pollution tolerant taxa Chironomus sp, Corbicula and Oligochaeta were present. Also notable was the absence of many native haplochromines and presence of mainly Brycinus sadleri, Oreochromis niloticus and leucostictus. The organs manifested high prevalence of severe inflammatory and regressive changes and higher organ indices that fell within the pathological category. These sites were consistently classified as highly polluted under the four endpoints. The reference site was classified as least polluted while Masese and Winday Bay were moderately polluted. Results suggested that the approach of using invertebrate and fish as bioindicators and the fish histopathology as a biomarker, in relation to water quality physicochemical variables was a useful tool in highlighting the spatial differences in environmental quality.
- Full Text:
- Date Issued: 2013
- Authors: Naigaga, Irene
- Date: 2013
- Subjects: Indicators (Biology) Biochemical markers Environmental monitoring -- Uganda Water quality biological assessment -- Uganda Water -- Pollution -- Uganda Wetlands -- Monitoring -- Uganda Wetland management -- Uganda Aquatic resources -- Uganda Aquatic resources conservation -- Uganda Aquatic resources -- Management -- Uganda Fishes -- Histopathaology -- Uganda Urban ecology (Biology) -- Uganda
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5198 , http://hdl.handle.net/10962/d1002603
- Description: Pollution of aquatic resources in Uganda is on the increase and the trends are expected to increase with increase in population size and urbanisation. Assessment and mitigation of the environmental impacts on water quality and biodiversity have now become necessary. The aim of the study was to integrate invertebrate and fish as bioindicators and fish histopathology as a biomarker in the assessment of water quality deterioration in urban wetlands in Uganda. The integration harnesses the advantages and counteracts the shortcomings of each method and thus builds a more robust diagnostic tool that gives a better view of the impacts to the entire ecosystem. Four endpoints which included, physicochemical variables, benthic macroinvertebrate bioindicators, fish bioindicators and fish histopathology biomarkers were compared between varied effluent-impacted wetlands (Murchison Bay in Kampala, and Kirinya, Masese and Winday Bay in Jinja) and a non-impacted reference wetland (Lwanika in Mayuge). Results from the effluent-impacted sites differed from the less impacted reference site. The two sampling locations at Murchison Bay (inshore and offshore) and one sampling location at Kirinya (inshore), that were highly impacted with urban effluent, showed elevated nutrient levels, low pH, dissolved oxygen and secchi depth readings. This corresponded with low invertebrate taxa and fish species diversity and richness; and severe histopathological responses in liver, gonads and gills of O. niloticus. Sensitive taxa such as ephemeroptera and trichoptera were completely absent while pollution tolerant taxa Chironomus sp, Corbicula and Oligochaeta were present. Also notable was the absence of many native haplochromines and presence of mainly Brycinus sadleri, Oreochromis niloticus and leucostictus. The organs manifested high prevalence of severe inflammatory and regressive changes and higher organ indices that fell within the pathological category. These sites were consistently classified as highly polluted under the four endpoints. The reference site was classified as least polluted while Masese and Winday Bay were moderately polluted. Results suggested that the approach of using invertebrate and fish as bioindicators and the fish histopathology as a biomarker, in relation to water quality physicochemical variables was a useful tool in highlighting the spatial differences in environmental quality.
- Full Text:
- Date Issued: 2013
Phylogeography and conservation of a newly identified galaxiid from the Joubertina area, South Africa
- Authors: Mataruse, Gamuchirai
- Date: 2013
- Subjects: Galaxiidae -- South Africa -- Joubertina , Phylogeography -- South Africa -- Joubertina , Galaxiidae -- Conservation -- South Africa -- Joubertina , Galaxiidae -- Effect of exotic animals on -- South Africa -- Joubertina , Galaxiidae -- Effect of habitat modification on -- South Africa -- Joubertina , Galaxiidae -- Genetics -- South Africa -- Joubertina , Galaxiidae -- Variation -- South Africa -- Joubertina , Galaxiidae -- Geographical distribution -- South Africa -- Joubertina
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5199 , http://hdl.handle.net/10962/d1003050 , Galaxiidae -- South Africa -- Joubertina , Phylogeography -- South Africa -- Joubertina , Galaxiidae -- Conservation -- South Africa -- Joubertina , Galaxiidae -- Effect of exotic animals on -- South Africa -- Joubertina , Galaxiidae -- Effect of habitat modification on -- South Africa -- Joubertina , Galaxiidae -- Genetics -- South Africa -- Joubertina , Galaxiidae -- Variation -- South Africa -- Joubertina , Galaxiidae -- Geographical distribution -- South Africa -- Joubertina
- Description: The dispersal of freshwater fishes in the Cape Floristic Region of South Africa has been attributed to river capture events and confluence of rivers during sea level regression. The role of low drainage divides and inter-basin water transfers have received less attention. A unique lineage of Galaxias zebratus (hereafter the Joubertina galaxias) occurs in two currently isolated river systems, the Gamtoos and Krom. The present study mapped the distribution of the Joubertina galaxias and used mitochondrial and nuclear DNA sequences to assess the processes that could have influenced its current distribution pattern. Analyses of both mitochondrial cytochrome ♭ and nuclear (S7) sequences revealed that observed genetic differentiation cannot be explained by isolation between the Gamtoos and Krom River systems. No genetic differentiation was found between the Krom River System and the Twee River (a tributary of the Gamtoos River System). Shallow genetic differentiation (0.4% for cytochrome ♭ and 0.3% for S7) was found between the Krom and the remaining populations in the Gamtoos River System. High levels of genetic structuring were observed within the Gamtoos River System with most tributaries having one or more unique alleles. Inter-basin dispersal during pluvial periods or recent human mediated translocation seems to be the most plausible explanations for presence of the Joubertina galaxias in the Krom River System. The present study also assessed the threats and habitat preferences of the Joubertina galaxias, and an evaluation of the conservation status of this lineage was done. The Joubertina galaxias is threatened mainly by alien fish invasion, habitat loss and loss of genetic diversity due to fragmentation of its populations. Due to its very restricted geographic range, small known population sizes and the intensity of threats to this lineage’s survival, this lineage has been assessed as Endangered. The lineage has a restricted Area of Occupancy (AOO) and Extent of Occurrence (EOO). The extent of occurrence has declined in all tributaries and is continuing to decline in all except two tributaries that are secure. The lineage may have had natural fragmentation among its populations, but recent threats have completely isolated the populations. The threats affect the lineage’s survival potential in the four tributaries which have small populations that are not presently viable. The densities observed for the Joubertina galaxias ranged from 0.16 - 1.3 fish /m² and the number of mature individuals for the whole population seems to be less than 2500 mature individuals. There is therefore a need for specific conservation actions to ensure the long-term survival of this unique lineage.
- Full Text:
- Date Issued: 2013
- Authors: Mataruse, Gamuchirai
- Date: 2013
- Subjects: Galaxiidae -- South Africa -- Joubertina , Phylogeography -- South Africa -- Joubertina , Galaxiidae -- Conservation -- South Africa -- Joubertina , Galaxiidae -- Effect of exotic animals on -- South Africa -- Joubertina , Galaxiidae -- Effect of habitat modification on -- South Africa -- Joubertina , Galaxiidae -- Genetics -- South Africa -- Joubertina , Galaxiidae -- Variation -- South Africa -- Joubertina , Galaxiidae -- Geographical distribution -- South Africa -- Joubertina
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5199 , http://hdl.handle.net/10962/d1003050 , Galaxiidae -- South Africa -- Joubertina , Phylogeography -- South Africa -- Joubertina , Galaxiidae -- Conservation -- South Africa -- Joubertina , Galaxiidae -- Effect of exotic animals on -- South Africa -- Joubertina , Galaxiidae -- Effect of habitat modification on -- South Africa -- Joubertina , Galaxiidae -- Genetics -- South Africa -- Joubertina , Galaxiidae -- Variation -- South Africa -- Joubertina , Galaxiidae -- Geographical distribution -- South Africa -- Joubertina
- Description: The dispersal of freshwater fishes in the Cape Floristic Region of South Africa has been attributed to river capture events and confluence of rivers during sea level regression. The role of low drainage divides and inter-basin water transfers have received less attention. A unique lineage of Galaxias zebratus (hereafter the Joubertina galaxias) occurs in two currently isolated river systems, the Gamtoos and Krom. The present study mapped the distribution of the Joubertina galaxias and used mitochondrial and nuclear DNA sequences to assess the processes that could have influenced its current distribution pattern. Analyses of both mitochondrial cytochrome ♭ and nuclear (S7) sequences revealed that observed genetic differentiation cannot be explained by isolation between the Gamtoos and Krom River systems. No genetic differentiation was found between the Krom River System and the Twee River (a tributary of the Gamtoos River System). Shallow genetic differentiation (0.4% for cytochrome ♭ and 0.3% for S7) was found between the Krom and the remaining populations in the Gamtoos River System. High levels of genetic structuring were observed within the Gamtoos River System with most tributaries having one or more unique alleles. Inter-basin dispersal during pluvial periods or recent human mediated translocation seems to be the most plausible explanations for presence of the Joubertina galaxias in the Krom River System. The present study also assessed the threats and habitat preferences of the Joubertina galaxias, and an evaluation of the conservation status of this lineage was done. The Joubertina galaxias is threatened mainly by alien fish invasion, habitat loss and loss of genetic diversity due to fragmentation of its populations. Due to its very restricted geographic range, small known population sizes and the intensity of threats to this lineage’s survival, this lineage has been assessed as Endangered. The lineage has a restricted Area of Occupancy (AOO) and Extent of Occurrence (EOO). The extent of occurrence has declined in all tributaries and is continuing to decline in all except two tributaries that are secure. The lineage may have had natural fragmentation among its populations, but recent threats have completely isolated the populations. The threats affect the lineage’s survival potential in the four tributaries which have small populations that are not presently viable. The densities observed for the Joubertina galaxias ranged from 0.16 - 1.3 fish /m² and the number of mature individuals for the whole population seems to be less than 2500 mature individuals. There is therefore a need for specific conservation actions to ensure the long-term survival of this unique lineage.
- Full Text:
- Date Issued: 2013
Life-history characteristics of an age-validated established invasive African sharptooth catfish, Clarias gariepinus, population in a warm–temperate African impoundment
- Wartenberg, Reece, Weyl, Olaf L F, Booth, Anthony J, Winker, A Henning
- Authors: Wartenberg, Reece , Weyl, Olaf L F , Booth, Anthony J , Winker, A Henning
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124921 , vital:35710 , https://doi.10.3377/004.048.0225
- Description: African sharptooth catfish Clarias gariepinus (Burchell, 1822) is a widely distributed fish that has now invaded water bodies in South America, Eastern Europe, Asia and South Africa (Cambray 2003). In South Africa it is native as far south as the Orange-Vaal river system, but inter-basin water transfer schemes (IBWTs), illegal stocking by anglers and from aquaculture has resulted in the establishment of extralimital populations in almost all river systems (van Rensburg et al. 2011). Within the Eastern Cape Province, C. gariepinus has invaded the Great Fish and Sundays rivers through IBWTs, that connect the Orange River to the Great Fish River and then to the Sundays River system which flows directly into Darlington Dam (Kadye & Booth 2013a) (Fig. 1). Soon after the completion of the IBWTs sharptooth catfish were recorded in Grassridge Dam in 1976 (Laurenson & Hocutt 1985), and later from Darlington Dam in 1981 (Scott et al. 2006). Although Cambray & Jubb (1977) are of the opinion that the species was translocated prior to the IBWT connection, there is now a permanent corridor between the Orange River and its receiving river systems that can facilitate the continued introduction of non-native Orange River fishes and other aquatic biota.
- Full Text:
- Date Issued: 2012
- Authors: Wartenberg, Reece , Weyl, Olaf L F , Booth, Anthony J , Winker, A Henning
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124921 , vital:35710 , https://doi.10.3377/004.048.0225
- Description: African sharptooth catfish Clarias gariepinus (Burchell, 1822) is a widely distributed fish that has now invaded water bodies in South America, Eastern Europe, Asia and South Africa (Cambray 2003). In South Africa it is native as far south as the Orange-Vaal river system, but inter-basin water transfer schemes (IBWTs), illegal stocking by anglers and from aquaculture has resulted in the establishment of extralimital populations in almost all river systems (van Rensburg et al. 2011). Within the Eastern Cape Province, C. gariepinus has invaded the Great Fish and Sundays rivers through IBWTs, that connect the Orange River to the Great Fish River and then to the Sundays River system which flows directly into Darlington Dam (Kadye & Booth 2013a) (Fig. 1). Soon after the completion of the IBWTs sharptooth catfish were recorded in Grassridge Dam in 1976 (Laurenson & Hocutt 1985), and later from Darlington Dam in 1981 (Scott et al. 2006). Although Cambray & Jubb (1977) are of the opinion that the species was translocated prior to the IBWT connection, there is now a permanent corridor between the Orange River and its receiving river systems that can facilitate the continued introduction of non-native Orange River fishes and other aquatic biota.
- Full Text:
- Date Issued: 2012
Gametogenesis, gonadal recrudescence, restraint and spawning patterns in Nile perch, Lates niloticus (Linnaeus, 1758)
- Authors: Kahwa, David
- Date: 2013
- Subjects: Nile perch -- Victoria, Lake Gametogenesis Oogenesis Spermatogenesis Nile perch -- Spawning -- Victoria, Lake Nile perch -- Induced spawning -- Victoria, Lake Nile perch -- Reproduction -- Endocrine aspects -- Victoria, Lake Fish culture -- Victoria, Lake
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5182 , http://hdl.handle.net/10962/d1001834
- Description: The Nile perch, Lates niloticus (Linnaeus, 1758), is a predacious freshwater fish widely distributed throughout the Afro-tropic eco-zone. The species was introduced to Lake Victoria in the early 1950s and by 1980 it had dominated the fisheries of Lake Victoria. This was followed by a dramatic decrease in the Nile perch fisheries production due to uncontrolled exploitation. The purpose of this thesis is to provide fundamental knowledge that can be applied in aquaculture and fisheries management through the study of the reproductive biology of L. niloticus. The research was aimed at the studying of the diverse aspects of the reproductive biology of L. niloticus in the Lake Victoria, Ugandan populations. This included reproductive patterns in relation to proximate environmental conditions, size at sexual maturity, gonad and gamete structure, gametogenesis and induced ovulation. The size at 50% sexual maturity for female Nile perch was 59.4 cm, which is lower than the earlier reported size of greater than 90 cm total length. Male L. niloticus matured at 57.8 cm total length in Lake Victoria. Microscopy revealed that L. niloticus from Lake Victoria had one spawning period that started in November and ended in March. Type I atresia occurred at high frequency from March to June, and type III atresia was present from July to September and between November and December. Spermatogenesis in L. niloticus is cystic and sperm development is the result of asynchronous activation of the germ cells. Type II spermatozoa are simple, uni-flagellate aquasperm with no acrosome. Oogenesis in L. niloticus differed from that of other fishes in that no cortical alveoli were present in any stage of oogenesis. Numerous oil globules were present in the primary yolk vesicle stage. This formed one centrally positioned, large oil globule in the tertiary yolk vesicle oocytes during final oocyte maturation. Clove oil was an effective sedative and an anaesthetic for the handling of L. niloticus. Induction time was more rapid at clove oil concentrations of 50 - 100 μl L⁻¹ than in fish exposed to clove oil concentrations less than 50 μl L⁻¹. Fish exposed to high concentrations exhibited significantly short induction times of less than 240 seconds. On average, fish recovered within 673 ± 58 seconds for all the concentrations used. Prolonged exposure of L. niloticus to low clove oil concentrations of 2.5 - 10 μl L⁻¹ did not change the blood plasma cortisol, glucose, and the lactate and chloride ion concentration, relative to the control treatment. Captive breeding was attempted by conducting induced spawning experiments. Only final oocyte maturation was achieved using a decapeptide Gonadotropin Releasing Hormone (Dargin, sGnRH-MET), combined with a water-soluble dopamine receptor antagonist metoclopramide. This thesis suggests a research approach that provides a basis for aquaculture of the new species by first studying reproductive biology patterns and then linking the information to gonad and gamete structure so that spawning times can be estimated. It further provides insights into aspects of the reproductive biology of the species and the effects of hormonal intervention on oocytes by showing at which stage of oocyte development hormones should be applied in L. niloticus. Clove oil can be used to sedate and anaesthetise L. niloticus broodfish to reduce the stress related to the handling of large specimens.
- Full Text:
- Date Issued: 2013
- Authors: Kahwa, David
- Date: 2013
- Subjects: Nile perch -- Victoria, Lake Gametogenesis Oogenesis Spermatogenesis Nile perch -- Spawning -- Victoria, Lake Nile perch -- Induced spawning -- Victoria, Lake Nile perch -- Reproduction -- Endocrine aspects -- Victoria, Lake Fish culture -- Victoria, Lake
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5182 , http://hdl.handle.net/10962/d1001834
- Description: The Nile perch, Lates niloticus (Linnaeus, 1758), is a predacious freshwater fish widely distributed throughout the Afro-tropic eco-zone. The species was introduced to Lake Victoria in the early 1950s and by 1980 it had dominated the fisheries of Lake Victoria. This was followed by a dramatic decrease in the Nile perch fisheries production due to uncontrolled exploitation. The purpose of this thesis is to provide fundamental knowledge that can be applied in aquaculture and fisheries management through the study of the reproductive biology of L. niloticus. The research was aimed at the studying of the diverse aspects of the reproductive biology of L. niloticus in the Lake Victoria, Ugandan populations. This included reproductive patterns in relation to proximate environmental conditions, size at sexual maturity, gonad and gamete structure, gametogenesis and induced ovulation. The size at 50% sexual maturity for female Nile perch was 59.4 cm, which is lower than the earlier reported size of greater than 90 cm total length. Male L. niloticus matured at 57.8 cm total length in Lake Victoria. Microscopy revealed that L. niloticus from Lake Victoria had one spawning period that started in November and ended in March. Type I atresia occurred at high frequency from March to June, and type III atresia was present from July to September and between November and December. Spermatogenesis in L. niloticus is cystic and sperm development is the result of asynchronous activation of the germ cells. Type II spermatozoa are simple, uni-flagellate aquasperm with no acrosome. Oogenesis in L. niloticus differed from that of other fishes in that no cortical alveoli were present in any stage of oogenesis. Numerous oil globules were present in the primary yolk vesicle stage. This formed one centrally positioned, large oil globule in the tertiary yolk vesicle oocytes during final oocyte maturation. Clove oil was an effective sedative and an anaesthetic for the handling of L. niloticus. Induction time was more rapid at clove oil concentrations of 50 - 100 μl L⁻¹ than in fish exposed to clove oil concentrations less than 50 μl L⁻¹. Fish exposed to high concentrations exhibited significantly short induction times of less than 240 seconds. On average, fish recovered within 673 ± 58 seconds for all the concentrations used. Prolonged exposure of L. niloticus to low clove oil concentrations of 2.5 - 10 μl L⁻¹ did not change the blood plasma cortisol, glucose, and the lactate and chloride ion concentration, relative to the control treatment. Captive breeding was attempted by conducting induced spawning experiments. Only final oocyte maturation was achieved using a decapeptide Gonadotropin Releasing Hormone (Dargin, sGnRH-MET), combined with a water-soluble dopamine receptor antagonist metoclopramide. This thesis suggests a research approach that provides a basis for aquaculture of the new species by first studying reproductive biology patterns and then linking the information to gonad and gamete structure so that spawning times can be estimated. It further provides insights into aspects of the reproductive biology of the species and the effects of hormonal intervention on oocytes by showing at which stage of oocyte development hormones should be applied in L. niloticus. Clove oil can be used to sedate and anaesthetise L. niloticus broodfish to reduce the stress related to the handling of large specimens.
- Full Text:
- Date Issued: 2013
Rhodes University Research Report 2013
- Rhodes University, Roberts, Jaine, Mantolo, Thumeka, Jacob, Patricia, Macgregor, Jill, Dore, Sally
- Authors: Rhodes University , Roberts, Jaine , Mantolo, Thumeka , Jacob, Patricia , Macgregor, Jill , Dore, Sally
- Date: 2013
- Language: English
- Type: Text
- Identifier: http://hdl.handle.net/10962/59330 , vital:27549
- Description: From Foreword by Dr Saleem Badat: Rhodes University has positioned itself as a research university that, alongside excellence in undergraduate teaching, also takes scholarship seriously. This has strongly shaped the intellectual identity of the university and, today, research income and expenditure are significant components of the university’s finances. Rhodes University values the scholar-teacher model of combining research with teaching and learning, and other scholarly activities. This has a strong influence on the quality of intellectual endeavour at the University, and is critical in advancing the University’s pursuit of a strong postgraduate trajectory. This is an opportunity to briefly reflect on research at Rhodes over the eight years of my Vice-Chancellorship. It is gratifying to see that scholarship and publishing has continued to blossom at Rhodes, and has also occurred over a wider academic base, and that there has also been increased enrolments of postgraduates, as part of overall University strategy. Postgraduate enrolments increased from 24% (1 397) in 2006 to 30% (2 302) in 2013, with considerable increases in the numbers of Masters and Doctoral students. Between 2006 and 2013, Honours and Postgraduate Diploma graduations increased from 453 to 719, Masters graduations increased by 73% (from 171 to 296) and Doctoral graduations by 70% (from 46 to 78). Concomitantly, there was an increase in the numbers of black and women PhD graduates. The number of Postdoctoral Fellows at Rhodes rose from 19 in 2007 to 68 in 2013, an increase of 258%. , A publication of the Rhodes University Research Office, compiled and edited by Jaine Roberts, Thumeka Mantolo, Patricia Jacob and Jill Macgregor. Design and Layout: Sally Dore
- Full Text:
- Date Issued: 2013
- Authors: Rhodes University , Roberts, Jaine , Mantolo, Thumeka , Jacob, Patricia , Macgregor, Jill , Dore, Sally
- Date: 2013
- Language: English
- Type: Text
- Identifier: http://hdl.handle.net/10962/59330 , vital:27549
- Description: From Foreword by Dr Saleem Badat: Rhodes University has positioned itself as a research university that, alongside excellence in undergraduate teaching, also takes scholarship seriously. This has strongly shaped the intellectual identity of the university and, today, research income and expenditure are significant components of the university’s finances. Rhodes University values the scholar-teacher model of combining research with teaching and learning, and other scholarly activities. This has a strong influence on the quality of intellectual endeavour at the University, and is critical in advancing the University’s pursuit of a strong postgraduate trajectory. This is an opportunity to briefly reflect on research at Rhodes over the eight years of my Vice-Chancellorship. It is gratifying to see that scholarship and publishing has continued to blossom at Rhodes, and has also occurred over a wider academic base, and that there has also been increased enrolments of postgraduates, as part of overall University strategy. Postgraduate enrolments increased from 24% (1 397) in 2006 to 30% (2 302) in 2013, with considerable increases in the numbers of Masters and Doctoral students. Between 2006 and 2013, Honours and Postgraduate Diploma graduations increased from 453 to 719, Masters graduations increased by 73% (from 171 to 296) and Doctoral graduations by 70% (from 46 to 78). Concomitantly, there was an increase in the numbers of black and women PhD graduates. The number of Postdoctoral Fellows at Rhodes rose from 19 in 2007 to 68 in 2013, an increase of 258%. , A publication of the Rhodes University Research Office, compiled and edited by Jaine Roberts, Thumeka Mantolo, Patricia Jacob and Jill Macgregor. Design and Layout: Sally Dore
- Full Text:
- Date Issued: 2013
Application of lie group analysis to mathematical models in epidemiology
- Authors: Otieno, Andrew Alex Omondi
- Date: 2013
- Subjects: Epidemiology -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:18486 , http://hdl.handle.net/11260/100
- Description: Lie group analysis is arguably the most systematic vehicle for finding exact solutions of differential equations. Using this approach one has at one's disposal a variety of algorithms that make the solution process of many differential equations algorithmic. Vital properties of a given differential equation can often be inferred from the symmetries admitted by the equation. However, Lie group analysis has not enjoyed wide-spread application to systems of first-order ordinary differential equations. This is because such systems typically admit an infinite number of Lie point symmetries, and there is no systematic way to find even a single nontrivial one-dimensional Lie symmetry algebra. In the few applications available, the approach has been to circumvent the problem by transforming a given system of first-order ordinary differential equations into one in which at least one of the equations is of order two or greater. It is therefore fair to say that the full power of Lie group analysis has not been sufficiently harnessed in the solution of systems of first-order ordinary differential equations. In this dissertation we review some applications of Lie group analysis to systems of first order ordinary differential equations. We shed light on the integration procedure for first-order systems of ordinary differential equations admitting a solvable Lie algebra. We do this via instructive examples drawn from mathematical epidemiology models. In particular we revisit the work of Nucci and Torrisi [54] and improve the exposition of the Lie-symmetry-inspired solution of a mathematical model which describes a HIV transmission. To aid implementation of the integration strategy for systems of ordinary differential equations, we have developed ad-hoc routines for finding particular types of admitted symmetries and checking if a given symmetry is indeed admitted by a system of ordinary differential equations.
- Full Text:
- Date Issued: 2013
- Authors: Otieno, Andrew Alex Omondi
- Date: 2013
- Subjects: Epidemiology -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:18486 , http://hdl.handle.net/11260/100
- Description: Lie group analysis is arguably the most systematic vehicle for finding exact solutions of differential equations. Using this approach one has at one's disposal a variety of algorithms that make the solution process of many differential equations algorithmic. Vital properties of a given differential equation can often be inferred from the symmetries admitted by the equation. However, Lie group analysis has not enjoyed wide-spread application to systems of first-order ordinary differential equations. This is because such systems typically admit an infinite number of Lie point symmetries, and there is no systematic way to find even a single nontrivial one-dimensional Lie symmetry algebra. In the few applications available, the approach has been to circumvent the problem by transforming a given system of first-order ordinary differential equations into one in which at least one of the equations is of order two or greater. It is therefore fair to say that the full power of Lie group analysis has not been sufficiently harnessed in the solution of systems of first-order ordinary differential equations. In this dissertation we review some applications of Lie group analysis to systems of first order ordinary differential equations. We shed light on the integration procedure for first-order systems of ordinary differential equations admitting a solvable Lie algebra. We do this via instructive examples drawn from mathematical epidemiology models. In particular we revisit the work of Nucci and Torrisi [54] and improve the exposition of the Lie-symmetry-inspired solution of a mathematical model which describes a HIV transmission. To aid implementation of the integration strategy for systems of ordinary differential equations, we have developed ad-hoc routines for finding particular types of admitted symmetries and checking if a given symmetry is indeed admitted by a system of ordinary differential equations.
- Full Text:
- Date Issued: 2013
Synthesis and characterisation of oxorhenium(V) and tricarbonylrhenium(I) complexes with biologically active N, O and N, S-Donor ligands
- Authors: Mukiza, Janvier
- Date: 2013
- Subjects: Rhenium , Rhenium compounds , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10437 , http://hdl.handle.net/10948/d1020769
- Description: This study investigated the synthesis of rhenium(I) and rhenium(V) complexes with a variety of multidentate NS, NSO, NO and SO-donor ligands. It also investigated the synthesis of dinuclear dihalogeno- and trihalogeno-bridged rhenium(I) complexes based on the fac-[Re(CO)3]+ core. The reactions of hydrated folic acid with [Re(CO)5X] (X = Cl, Br) were studied, and the complexes [Re(CO)3(H2O)3]+[Re2(μ-X)3CO)6]−.5H2O [X= Br (1), Cl(2)] were isolated. The reaction of orotic acid potassium salt [Re(CO)5Br] was performed, and the complex [Re2(μ-Br)2(CO)8] was isolated. The reaction of bis(piperidin-1- yl)methanone with [Re(CO)5Cl] followed by recrystallisation of the resulting precipitate in dichloromethane/acetontrile resulted in the complex [Re2(μ- Cl)2(CO)6(MeCN)2]. The X-ray crystal structures show that all these complexes display a distorted octahedral geometry around the central rhenium atoms. The reactions of aroylhydrazone-based ligands such as 3-((pyridin- 2yl)methyleneamino)-2,3-dihydro-2-pyridin-2yl)quinazolin-4-(1H)-one (Hppq) and N-(di(pyridin-2-yl)methylene)benzohydrazide (Hdpmb) with [Re(CO)5Cl] were studied and led to the formation of the complexes [Re(CO)3Cl(Hdpmb)] and [Re(CO)3Cl(Hppq)]. The Hdpmb and Hppq coordinated to the fac-[Re(CO)3]+ core as neutral bidentate chalates via the pyridinic nitrogens (for Hdpmb) and via imino and pyridinic nitrogens for Hppq. The X-ray crystal structures show that the geometry around the rhenium in both complexes is a distorted octahedral. The treatment of the dithizone (H2dz) ligand with rhenium(V) precursors containing a triphenylphosphine group (PPh3) led to the decomposition of dithizone. The decomposition product reacted with the triphenylphosphine group and generated a new ligand triphenylphosphazeno-N-phenylmethanethiohydrazide (H2L). The reaction of trans-[ReOX3(PPh3)2] (X = Cl, Br) with dithizone (H2dz) led to the complex [ReO(dz)2][ReO(HL)2]. The reaction of trans-[ReOI2(OEt)(PPh3)2] with H2dz led to the same product. The reaction of cis-[ReO2I(PPh3)2] with H2dz in methanol led to [ReO(dz)2][ReO(HL)2](MeOH)2 in which methanol bonded to HLvia hydrogen bonds. The H2dz was doubly deprotonated and coordinated to the [ReO]3+ moiety via a thiolate sulfur and deprotonated hydrazinic nitrogen to yield [ReO(dz)2]−, while the H2L was singly deprotonated and coordinated to [ReO]3+ moiety via the neutral sulfur atom and deprotonated hydrazinic nitrogen to yield [ReO(HL)2]+. The X-ray crystal structure show that in both [ReO(HL)2]+ and [ReO(dz)2]−, the rhenium atoms are five-coordinated and adopt a distorted squarebased pyramidal geometry. The reaction of thiosemicarbazones such as salcylidene-4- phenylthiosemicarbazide (H3salpt) with cis-[ReO2I(PPh3)2] was investigated and led to the complex [ReO(Hsalpt)(H2salpt)]. The X-ray study reveals that Hsalpt is present as a tridentate chelate coordinating via the thiolate sulfur, imino nitrogen and phenolic oxygen, while H2salpt coordinates as a bidentate chelate via the thiolate sulfur and imino nitrogen atoms. The geometry around rhenium is distorted octahedral. The coordination mode of the benzoylthiourea derivatives 4-tert-butyl-N- (diphenylcarbamothioyl)benzamide (Htpb) and N-(diethylcarbamothioyl)benzamide (Heb) to the [Re2O3]4+ and fac-[Re(CO)3]+ cores were investigated. The reaction of [Re(CO)5Cl] in presence of sodium acetate with Htpb led to the dimeric complex [Re(CO)3(tpb)]2 in which the tpb coordinated to the fac-[Re(CO)3]+ core via the ketonic oxygen and bridging thiolate sulfur. The same reaction with Heb led to the monomeric complex [Re(CO)3(eb)(Heb)], in which the eb coordinates to the fac-[Re(CO)3]+core via thiolate sulfur and ketonic oxygen with Heb binding via the neutral sulfur atom. The reaction of Heb with cis-[ReO2I(PPh3)2] at room temperature with excess of sodium acetate led to the dimeric complex (μ-O)[ReO(eb)2]2 in which Heb is present as a monoanionic (deprotonated) bidentate with coordination through the thiolate sulfur and ketonic oxygen.
- Full Text:
- Date Issued: 2013
- Authors: Mukiza, Janvier
- Date: 2013
- Subjects: Rhenium , Rhenium compounds , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10437 , http://hdl.handle.net/10948/d1020769
- Description: This study investigated the synthesis of rhenium(I) and rhenium(V) complexes with a variety of multidentate NS, NSO, NO and SO-donor ligands. It also investigated the synthesis of dinuclear dihalogeno- and trihalogeno-bridged rhenium(I) complexes based on the fac-[Re(CO)3]+ core. The reactions of hydrated folic acid with [Re(CO)5X] (X = Cl, Br) were studied, and the complexes [Re(CO)3(H2O)3]+[Re2(μ-X)3CO)6]−.5H2O [X= Br (1), Cl(2)] were isolated. The reaction of orotic acid potassium salt [Re(CO)5Br] was performed, and the complex [Re2(μ-Br)2(CO)8] was isolated. The reaction of bis(piperidin-1- yl)methanone with [Re(CO)5Cl] followed by recrystallisation of the resulting precipitate in dichloromethane/acetontrile resulted in the complex [Re2(μ- Cl)2(CO)6(MeCN)2]. The X-ray crystal structures show that all these complexes display a distorted octahedral geometry around the central rhenium atoms. The reactions of aroylhydrazone-based ligands such as 3-((pyridin- 2yl)methyleneamino)-2,3-dihydro-2-pyridin-2yl)quinazolin-4-(1H)-one (Hppq) and N-(di(pyridin-2-yl)methylene)benzohydrazide (Hdpmb) with [Re(CO)5Cl] were studied and led to the formation of the complexes [Re(CO)3Cl(Hdpmb)] and [Re(CO)3Cl(Hppq)]. The Hdpmb and Hppq coordinated to the fac-[Re(CO)3]+ core as neutral bidentate chalates via the pyridinic nitrogens (for Hdpmb) and via imino and pyridinic nitrogens for Hppq. The X-ray crystal structures show that the geometry around the rhenium in both complexes is a distorted octahedral. The treatment of the dithizone (H2dz) ligand with rhenium(V) precursors containing a triphenylphosphine group (PPh3) led to the decomposition of dithizone. The decomposition product reacted with the triphenylphosphine group and generated a new ligand triphenylphosphazeno-N-phenylmethanethiohydrazide (H2L). The reaction of trans-[ReOX3(PPh3)2] (X = Cl, Br) with dithizone (H2dz) led to the complex [ReO(dz)2][ReO(HL)2]. The reaction of trans-[ReOI2(OEt)(PPh3)2] with H2dz led to the same product. The reaction of cis-[ReO2I(PPh3)2] with H2dz in methanol led to [ReO(dz)2][ReO(HL)2](MeOH)2 in which methanol bonded to HLvia hydrogen bonds. The H2dz was doubly deprotonated and coordinated to the [ReO]3+ moiety via a thiolate sulfur and deprotonated hydrazinic nitrogen to yield [ReO(dz)2]−, while the H2L was singly deprotonated and coordinated to [ReO]3+ moiety via the neutral sulfur atom and deprotonated hydrazinic nitrogen to yield [ReO(HL)2]+. The X-ray crystal structure show that in both [ReO(HL)2]+ and [ReO(dz)2]−, the rhenium atoms are five-coordinated and adopt a distorted squarebased pyramidal geometry. The reaction of thiosemicarbazones such as salcylidene-4- phenylthiosemicarbazide (H3salpt) with cis-[ReO2I(PPh3)2] was investigated and led to the complex [ReO(Hsalpt)(H2salpt)]. The X-ray study reveals that Hsalpt is present as a tridentate chelate coordinating via the thiolate sulfur, imino nitrogen and phenolic oxygen, while H2salpt coordinates as a bidentate chelate via the thiolate sulfur and imino nitrogen atoms. The geometry around rhenium is distorted octahedral. The coordination mode of the benzoylthiourea derivatives 4-tert-butyl-N- (diphenylcarbamothioyl)benzamide (Htpb) and N-(diethylcarbamothioyl)benzamide (Heb) to the [Re2O3]4+ and fac-[Re(CO)3]+ cores were investigated. The reaction of [Re(CO)5Cl] in presence of sodium acetate with Htpb led to the dimeric complex [Re(CO)3(tpb)]2 in which the tpb coordinated to the fac-[Re(CO)3]+ core via the ketonic oxygen and bridging thiolate sulfur. The same reaction with Heb led to the monomeric complex [Re(CO)3(eb)(Heb)], in which the eb coordinates to the fac-[Re(CO)3]+core via thiolate sulfur and ketonic oxygen with Heb binding via the neutral sulfur atom. The reaction of Heb with cis-[ReO2I(PPh3)2] at room temperature with excess of sodium acetate led to the dimeric complex (μ-O)[ReO(eb)2]2 in which Heb is present as a monoanionic (deprotonated) bidentate with coordination through the thiolate sulfur and ketonic oxygen.
- Full Text:
- Date Issued: 2013
Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands
- Authors: Habarurema, Gratien
- Date: 2013
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10441 , http://hdl.handle.net/10948/d1020952
- Description: This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the synthesis of tridentate, tetradentate and pentadentate Schiff bases ligands derived from the condensation reactions of benzaldehyde with different primary amines. The structures of these Schiff bases and their complexes were confirmed by using physical characterization methods, namely melting points, UV-Visible, UV-emission, 1H NMR and IR spectroscopy, X-ray diffractometry and elemental analysis. To further understand the coordination chemistry of rhenium, the prepared diiminediphenol N2O2-donor Schiff base ligand N N′-o-phenylene-bis(salicylaldimine) (H2salphen) was reacted with trans-[ReOCl3(PPh3)2] to yield cis-[ReCl2(ophsal)(PPh3)], whereas its reaction with trans-[ReOBr3(PPh3)2] resulted in the formation of the cis-[ReBr2(aphsal)(PPh3)].2CH3CN complex. In the above complexes the H2salphen ligand was cleaved leading to the coordinated tridentate ophsal NO2- and aphsal N2O-donor ligands. The reaction of H3aphsal with trans-[ReOBr3(PPh3)2] in toluene led to an unexpected compound, trans- [{[ReBr(aphsal)(PPh3)2]Br}{[ReBr(aphsal)(PPh3)2](ReO4)}] with an imido [ReNR]3+core. The ligand aphsal was coordinated tridentately with the doubly deprotonated amino nitrogen leading to Re(V)-imido complexes. The reaction of 2-((Z)-(2-aminoethylimino)methyl)phenol (H3amphol) with [Re(CO)5Cl] led to the rhenium(I) product fac-[Re(CO)3(H3amphol)] with H3amphol coordinated as a monoanionic tridentate chelate through its phenolate oxygen and amino nitrogen atoms. The X-ray crystal structures showed that all complexes display a distorted octahedral geometry around the central rhenium atom. The reaction of 2,6-bis(2-hydroxyphenylimino)pyridine (H2hpp) with cis-[ReO2I(PPh3)2] resulted in the reduced Re(III) product trans-[Re(hpp)(PPh3)2]I, while trans-[Re(hpp)(PPh3)2](ReO4) was isolated from its reaction with trans-[ReOCl3(PPh3)2]. The H2hpp ligand acts as a pentadentate N3O2-donor ligand where the two phenolic protons undergo deprotonation and its three nitrogens act as neutral donor atoms. Both compounds resulted from a disproportionation reaction characterized by the produced perrhenate counter-ion. The complex fac-[Re(CO)3(H2hpp)Cl] was prepared from [Re(CO)5Cl] and H2hpp in toluene. The H2hpp ligand acted as a neutral bidentate N,N-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, two neutral nitrogen atoms and a chloride ligand. The reactions of the potentially tetradentate ligand N,N'-ethylenebis(salicylideneimine) (H2salen) with different rhenium(V) precursors resulted in the formation of two dimeric oxorhenium (V) compounds. In the reaction of H2salen with trans-[ReOCl3(PPh3)2] in ethanol, the highly unusual distorted dimeric complex (μ-salen)[ReOCl2(PPh3)]2 was isolated, in which salen2- is coordinated as a tetradentate to two oxorhenium(V) centres, and salen2- is present as a bidentate monoanionic ligand on each rhenium center. The reaction of cis- [ReO2I(PPh3)2] with H2salen led to the formation of the neutral dimeric oxorhenium(V) complex (μ-O)[ReO(salen)]2 in which the tetradentate chelate salen acts as a tetradentate dianionic ligand through its phenolate oxygens and nitrogen atoms of the azomethine groups. In its reaction with H2hmp the compound (μ-O)[ReO(hmp)]2 was isolated. In this product the pentadentate ligand H2hmp coordinated as tetradentate via its phenolic oxygen and nitrogen atoms. The reaction of the potentially tetradentate N1,N2-bis(aminobenzylidene)-1,2-ethylenediamine (H2amben) with trans-[ReOCl3(PPh3)2] led to the formation of the monocationic square-pyramidal complex salt [ReO(amben)](ReO4.
- Full Text:
- Date Issued: 2013
- Authors: Habarurema, Gratien
- Date: 2013
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10441 , http://hdl.handle.net/10948/d1020952
- Description: This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the synthesis of tridentate, tetradentate and pentadentate Schiff bases ligands derived from the condensation reactions of benzaldehyde with different primary amines. The structures of these Schiff bases and their complexes were confirmed by using physical characterization methods, namely melting points, UV-Visible, UV-emission, 1H NMR and IR spectroscopy, X-ray diffractometry and elemental analysis. To further understand the coordination chemistry of rhenium, the prepared diiminediphenol N2O2-donor Schiff base ligand N N′-o-phenylene-bis(salicylaldimine) (H2salphen) was reacted with trans-[ReOCl3(PPh3)2] to yield cis-[ReCl2(ophsal)(PPh3)], whereas its reaction with trans-[ReOBr3(PPh3)2] resulted in the formation of the cis-[ReBr2(aphsal)(PPh3)].2CH3CN complex. In the above complexes the H2salphen ligand was cleaved leading to the coordinated tridentate ophsal NO2- and aphsal N2O-donor ligands. The reaction of H3aphsal with trans-[ReOBr3(PPh3)2] in toluene led to an unexpected compound, trans- [{[ReBr(aphsal)(PPh3)2]Br}{[ReBr(aphsal)(PPh3)2](ReO4)}] with an imido [ReNR]3+core. The ligand aphsal was coordinated tridentately with the doubly deprotonated amino nitrogen leading to Re(V)-imido complexes. The reaction of 2-((Z)-(2-aminoethylimino)methyl)phenol (H3amphol) with [Re(CO)5Cl] led to the rhenium(I) product fac-[Re(CO)3(H3amphol)] with H3amphol coordinated as a monoanionic tridentate chelate through its phenolate oxygen and amino nitrogen atoms. The X-ray crystal structures showed that all complexes display a distorted octahedral geometry around the central rhenium atom. The reaction of 2,6-bis(2-hydroxyphenylimino)pyridine (H2hpp) with cis-[ReO2I(PPh3)2] resulted in the reduced Re(III) product trans-[Re(hpp)(PPh3)2]I, while trans-[Re(hpp)(PPh3)2](ReO4) was isolated from its reaction with trans-[ReOCl3(PPh3)2]. The H2hpp ligand acts as a pentadentate N3O2-donor ligand where the two phenolic protons undergo deprotonation and its three nitrogens act as neutral donor atoms. Both compounds resulted from a disproportionation reaction characterized by the produced perrhenate counter-ion. The complex fac-[Re(CO)3(H2hpp)Cl] was prepared from [Re(CO)5Cl] and H2hpp in toluene. The H2hpp ligand acted as a neutral bidentate N,N-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, two neutral nitrogen atoms and a chloride ligand. The reactions of the potentially tetradentate ligand N,N'-ethylenebis(salicylideneimine) (H2salen) with different rhenium(V) precursors resulted in the formation of two dimeric oxorhenium (V) compounds. In the reaction of H2salen with trans-[ReOCl3(PPh3)2] in ethanol, the highly unusual distorted dimeric complex (μ-salen)[ReOCl2(PPh3)]2 was isolated, in which salen2- is coordinated as a tetradentate to two oxorhenium(V) centres, and salen2- is present as a bidentate monoanionic ligand on each rhenium center. The reaction of cis- [ReO2I(PPh3)2] with H2salen led to the formation of the neutral dimeric oxorhenium(V) complex (μ-O)[ReO(salen)]2 in which the tetradentate chelate salen acts as a tetradentate dianionic ligand through its phenolate oxygens and nitrogen atoms of the azomethine groups. In its reaction with H2hmp the compound (μ-O)[ReO(hmp)]2 was isolated. In this product the pentadentate ligand H2hmp coordinated as tetradentate via its phenolic oxygen and nitrogen atoms. The reaction of the potentially tetradentate N1,N2-bis(aminobenzylidene)-1,2-ethylenediamine (H2amben) with trans-[ReOCl3(PPh3)2] led to the formation of the monocationic square-pyramidal complex salt [ReO(amben)](ReO4.
- Full Text:
- Date Issued: 2013
Photophysicochemical properties of aluminium phthalocyanine-platinum conjugates
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
Financial management practices employed by small and medium enterprises (SMES) in the Buffalo City Metropolitan Municipality, Eastern Cape
- Authors: Marembo, Mathew
- Date: 2013
- Subjects: Small business -- South Africa -- Eastern Cape -- Finance , Small business -- South Africa -- Eastern Cape -- Management
- Language: English
- Type: Thesis , Masters , M Com (Business Management)
- Identifier: vital:11325 , http://hdl.handle.net/10353/d1013583 , Small business -- South Africa -- Eastern Cape -- Finance , Small business -- South Africa -- Eastern Cape -- Management
- Description: This study examined how financial management decisions are made by small and medium enterprises (SMEs) in the Buffalo City Metropolitan in Eastern Cape, South Africa. The study aimed at discovering SME awareness on financial management practices. The financial management practices address issues on capital budgeting, working capital management, capital structure, financial reporting and analysis. The study, therefore, hypothesised that SMEs were not aware of the sound financial management practices. It was also intended in this study to examine the relationship between employment of sound financial management practices and firm financial performance. Subsequently, the study hypothesised that the employment of sound financial management practices by SMEs did not significantly affect their financial performance. The results obtained in this study revealed that SMEs were aware of the sound financial management practices that could be employed to yield high financial performance. However, the results also revealed that most SMEs were not employing qualified personnel and this in turn had an effect on the effectiveness of the financial management practices that the SMEs utilised. The findings also indicated that the employment of sound financial management practices did significantly and positively affect the financial performance of SMEs. The study recommended that SMEs could increase their chances of financial survival if they employ sound financial management practices. The study also gave recommendations to the South African Government to provide effective facilities and services to SMEs and help sustain them because they are important in the economy. Lastly, the study recommended financial institutions to relax their credit granting policies so that SMEs could access funds.
- Full Text:
- Date Issued: 2013
- Authors: Marembo, Mathew
- Date: 2013
- Subjects: Small business -- South Africa -- Eastern Cape -- Finance , Small business -- South Africa -- Eastern Cape -- Management
- Language: English
- Type: Thesis , Masters , M Com (Business Management)
- Identifier: vital:11325 , http://hdl.handle.net/10353/d1013583 , Small business -- South Africa -- Eastern Cape -- Finance , Small business -- South Africa -- Eastern Cape -- Management
- Description: This study examined how financial management decisions are made by small and medium enterprises (SMEs) in the Buffalo City Metropolitan in Eastern Cape, South Africa. The study aimed at discovering SME awareness on financial management practices. The financial management practices address issues on capital budgeting, working capital management, capital structure, financial reporting and analysis. The study, therefore, hypothesised that SMEs were not aware of the sound financial management practices. It was also intended in this study to examine the relationship between employment of sound financial management practices and firm financial performance. Subsequently, the study hypothesised that the employment of sound financial management practices by SMEs did not significantly affect their financial performance. The results obtained in this study revealed that SMEs were aware of the sound financial management practices that could be employed to yield high financial performance. However, the results also revealed that most SMEs were not employing qualified personnel and this in turn had an effect on the effectiveness of the financial management practices that the SMEs utilised. The findings also indicated that the employment of sound financial management practices did significantly and positively affect the financial performance of SMEs. The study recommended that SMEs could increase their chances of financial survival if they employ sound financial management practices. The study also gave recommendations to the South African Government to provide effective facilities and services to SMEs and help sustain them because they are important in the economy. Lastly, the study recommended financial institutions to relax their credit granting policies so that SMEs could access funds.
- Full Text:
- Date Issued: 2013
Novel applications of Morita-Baylis-Hillman methodology in organic synthesis
- Authors: Mciteka, Lulama Patrick
- Date: 2013 , 2013-04-22
- Subjects: Organic compounds -- Synthesis -- Research Asymmetric synthesis Asymmetry (Chemistry) Chemical reactions -- Research Camphor -- Research AZT (Drug) -- Research Chemical inhibitors -- Research Chemistry -- Methodology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4439 , http://hdl.handle.net/10962/d1007598
- Description: The overall approach in the present investigation has been to explore applications of the Morita-Baylis-Hillman (MBH) reaction in asymmetric synthesis and in the continuation of systems with medicinal potential. To this end, a series of varied camphor-derived acrylate esters was prepared to serve as chiral substrates in asymmetric Morita-Baylis- Hillman reactions. Reduction of N-substituted camphor-10-sulfonamides afforded the 3- exo-hydroxy derivatives as the major products. Acylation of the corresponding sodium alkoxides gave the desired 3-exo-acrylate esters, isolation of which was complicated by concomitant formation of hydrochlorinated and diastereomeric competition products. Bulky camphorsulfonamides containing alkyl, dialkyl, aromatic and adamantyl groups were selected as N-substituents with the view of achieving stereoselective outcome in subsequent MBH reactions. The synthesis of novel camphor-derived Morita-Baylis-Hillman adducts using various pyridine-carboxaldehydes proceeded with exceptionally high yields with diastereoselectivities ranging from 7-33 % d.e. Both 1D and 2D NMR and HRMS techniques were employed to confirm the structures and an extensive study of the electropositive fragmentation patterns of a number of camphor-derived chiral acrylate esters was conducted. Attention has also been given to the application of MBH methodology in the construction of heterocyclic ‘cinnamate-like’ AZT conjugates which were designed to serve as dualaction HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. A number of pyridine carboxaldehyde-derived MBH adducts were synthesized using methyl, ethyl and t-butyl acrylates in the presence of 3-hydroxyquinuclidine (3-HQ) as catalyst. The yields for these reactions were excellent. The resulting MBH adducts were acetylated and subjected to aza-Michael addition using propargylamine. The resulting alkylamino compounds were then used in ‘Click reactions’ to form the targeted AZT-conjugates in moderate to excellent yield. In silico docking of computer modelled AZT-conjugates into the HIV-1 integrase and reverse transcriptase enzyme-active sites and potential hydrogen-bonding interaction with active-site amino acid residues were identified. The electrospray MS fragmentations of the AZT and the novel AZT-conjugates were also investigated and common fragmentation pathways were identified.
- Full Text:
- Date Issued: 2013
- Authors: Mciteka, Lulama Patrick
- Date: 2013 , 2013-04-22
- Subjects: Organic compounds -- Synthesis -- Research Asymmetric synthesis Asymmetry (Chemistry) Chemical reactions -- Research Camphor -- Research AZT (Drug) -- Research Chemical inhibitors -- Research Chemistry -- Methodology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4439 , http://hdl.handle.net/10962/d1007598
- Description: The overall approach in the present investigation has been to explore applications of the Morita-Baylis-Hillman (MBH) reaction in asymmetric synthesis and in the continuation of systems with medicinal potential. To this end, a series of varied camphor-derived acrylate esters was prepared to serve as chiral substrates in asymmetric Morita-Baylis- Hillman reactions. Reduction of N-substituted camphor-10-sulfonamides afforded the 3- exo-hydroxy derivatives as the major products. Acylation of the corresponding sodium alkoxides gave the desired 3-exo-acrylate esters, isolation of which was complicated by concomitant formation of hydrochlorinated and diastereomeric competition products. Bulky camphorsulfonamides containing alkyl, dialkyl, aromatic and adamantyl groups were selected as N-substituents with the view of achieving stereoselective outcome in subsequent MBH reactions. The synthesis of novel camphor-derived Morita-Baylis-Hillman adducts using various pyridine-carboxaldehydes proceeded with exceptionally high yields with diastereoselectivities ranging from 7-33 % d.e. Both 1D and 2D NMR and HRMS techniques were employed to confirm the structures and an extensive study of the electropositive fragmentation patterns of a number of camphor-derived chiral acrylate esters was conducted. Attention has also been given to the application of MBH methodology in the construction of heterocyclic ‘cinnamate-like’ AZT conjugates which were designed to serve as dualaction HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. A number of pyridine carboxaldehyde-derived MBH adducts were synthesized using methyl, ethyl and t-butyl acrylates in the presence of 3-hydroxyquinuclidine (3-HQ) as catalyst. The yields for these reactions were excellent. The resulting MBH adducts were acetylated and subjected to aza-Michael addition using propargylamine. The resulting alkylamino compounds were then used in ‘Click reactions’ to form the targeted AZT-conjugates in moderate to excellent yield. In silico docking of computer modelled AZT-conjugates into the HIV-1 integrase and reverse transcriptase enzyme-active sites and potential hydrogen-bonding interaction with active-site amino acid residues were identified. The electrospray MS fragmentations of the AZT and the novel AZT-conjugates were also investigated and common fragmentation pathways were identified.
- Full Text:
- Date Issued: 2013
A study of maximum and minimum operators with applications to piecewise linear payoff functions
- Authors: Seedat, Ebrahim
- Date: 2013
- Subjects: Options (Finance) Piecewise linear topology Geometry, Affine Riesz spaces Lattice theory Algebra, Boolean Pricing , Max and min operators
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:931 , http://hdl.handle.net/10962/d1001457
- Description: The payoff functions of contingent claims (options) of one variable are prominent in Financial Economics and thus assume a fundamental role in option pricing theory. Some of these payoff functions are continuous, piecewise-defined and linear or affine. Such option payoff functions can be analysed in a useful way when they are represented in additive, Boolean normal, graphical and linear form. The issue of converting such payoff functions expressed in the additive, linear or graphical form into an equivalent Boolean normal form, has been considered by several authors for more than half-a-century to better-understand the role of such functions. One aspect of our study is to unify the foregoing different forms of representation, by creating algorithms that convert a payoff function expressed in graphical form into Boolean normal form and then into the additive form and vice versa. Applications of these algorithms are considered in a general theoretical sense and also in the context of specific option contracts wherever relevant. The use of these algorithms have yielded easy computation of the area enclosed by the graph of various functions using min and max operators in several ways, which, in our opinion, are important in option pricing. To summarise, this study effectively dealt with maximum and minimum operators from several perspectives
- Full Text:
- Date Issued: 2013
- Authors: Seedat, Ebrahim
- Date: 2013
- Subjects: Options (Finance) Piecewise linear topology Geometry, Affine Riesz spaces Lattice theory Algebra, Boolean Pricing , Max and min operators
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:931 , http://hdl.handle.net/10962/d1001457
- Description: The payoff functions of contingent claims (options) of one variable are prominent in Financial Economics and thus assume a fundamental role in option pricing theory. Some of these payoff functions are continuous, piecewise-defined and linear or affine. Such option payoff functions can be analysed in a useful way when they are represented in additive, Boolean normal, graphical and linear form. The issue of converting such payoff functions expressed in the additive, linear or graphical form into an equivalent Boolean normal form, has been considered by several authors for more than half-a-century to better-understand the role of such functions. One aspect of our study is to unify the foregoing different forms of representation, by creating algorithms that convert a payoff function expressed in graphical form into Boolean normal form and then into the additive form and vice versa. Applications of these algorithms are considered in a general theoretical sense and also in the context of specific option contracts wherever relevant. The use of these algorithms have yielded easy computation of the area enclosed by the graph of various functions using min and max operators in several ways, which, in our opinion, are important in option pricing. To summarise, this study effectively dealt with maximum and minimum operators from several perspectives
- Full Text:
- Date Issued: 2013
Synthesis of fluorescent polymers with pendant triazole-substituted coumarin side-chains via a combination of click chemistry and raft-mediated polymerization
- Authors: Wali, Nwabisa Whitney
- Date: 2013
- Subjects: Fluorescent polymers , Polymerization , Macromolecules -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10432 , http://hdl.handle.net/10948/d1020142
- Description: This research project focuses on the synthesis of fluorescent polymers with pendant triazole-substituted coumarin side chain units. Copper(I)-catalyzed Huisgen’s 1,3-dipolar cycloaddition of alkynes with azides to form a 1,2,3-triazole ring, a typical example of “click” reaction, has been utilized for the synthesis of a novel vinyl monomer, 2-oxo-3-(4- vinyl-1H-1,2,3-triazol-1-yl)-2H-chromen-7-yl acetate 62. The monomer and its precursors were synthesised and characterized using 1D- and 2D-NMR and FT-IR. Coumarin-containing triazole polymers were synthesised using free radical polymerization. Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated polymerization was used to synthesise well defined coumarin-containing triazole polymers with moderate PDI values. The polymers were characterised using 1H-NMR and FT-IR. Modelling of the monomer precursor 61 and the monomer 62 at DFT level of approximation provided useful insights into possible conformations adopted by the monomer precursor 61 and the monomer 62. The photophysical properties of the novel monomer and the synthesised polymers were investigated in a polar solvent.
- Full Text:
- Date Issued: 2013
- Authors: Wali, Nwabisa Whitney
- Date: 2013
- Subjects: Fluorescent polymers , Polymerization , Macromolecules -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10432 , http://hdl.handle.net/10948/d1020142
- Description: This research project focuses on the synthesis of fluorescent polymers with pendant triazole-substituted coumarin side chain units. Copper(I)-catalyzed Huisgen’s 1,3-dipolar cycloaddition of alkynes with azides to form a 1,2,3-triazole ring, a typical example of “click” reaction, has been utilized for the synthesis of a novel vinyl monomer, 2-oxo-3-(4- vinyl-1H-1,2,3-triazol-1-yl)-2H-chromen-7-yl acetate 62. The monomer and its precursors were synthesised and characterized using 1D- and 2D-NMR and FT-IR. Coumarin-containing triazole polymers were synthesised using free radical polymerization. Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated polymerization was used to synthesise well defined coumarin-containing triazole polymers with moderate PDI values. The polymers were characterised using 1H-NMR and FT-IR. Modelling of the monomer precursor 61 and the monomer 62 at DFT level of approximation provided useful insights into possible conformations adopted by the monomer precursor 61 and the monomer 62. The photophysical properties of the novel monomer and the synthesised polymers were investigated in a polar solvent.
- Full Text:
- Date Issued: 2013
A marine chemical ecology study of the sea hare, Bursatella leachii in South Africa
- Authors: D'Souza, Nicole
- Date: 2013 , 2013-03-22
- Subjects: Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4283 , http://hdl.handle.net/10962/d1002952 , Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Description: The large cosmopolitan sea hare Bursatella leachii is a common resident in Eastern Cape river mouths during summer and late autumn where they congregate in beds of Zostera capensis to breed. In this thesis, the previously known toxic formamide marine secondary metabolite (-)-bursatellin (2.2), which may deter predators of South African specimens of the globally distributed sea hare Bursatella leachii, was isolated and identified (Chapter 2). There have been no previous chemical ecology studies of B. leachii and the latter half of this thesis is devoted to chemical ecology studies of this organism. Interestingly, the isolation of the (-)-diastereomer of 2.2 from specimens of B. leachii collected from the Kariega River mouth (near Kenton-on-Sea) suggests that the South African specimens of this species are similar to specimens collected from Puerto Rico and from the Mediterranean Sea. Two different chromatographic techniques for isolating 2.2 were compared in order to maximize the amount of 2.2 isolated from the Kariega River mouth sea hares. The doubling of selected resonances observed in both the ¹H and ¹³C NMR spectra of the bursatellin isolated in this study suggest one of three possibilities; either firstly, the presence of closely related compound(s), secondly, the presence of diastereomers or thirdly the presence of rotamers. Through NMR kinetic studies, we were able to establish that the presence of rotamers was very unlikely due to no change in the relative ratio (3:1) of the ¹H NMR signals with an increase in temperature. Although the attempted synthesis of the acetate derivative (2.28), as a means of separating a diastereomeric mixture was successful, the chromatographic separation of the proposed acetylated diastereomers was not successful. Preparation of the camphanate ester derivatives (e.g. 2.30) proved to be unsuccessful. Five B. leachii specimens were dissected, their organs separated and individually extracted with methanol. The methanol extracts were individually chromatographed on HP-20 media, and the distribution of bursatellin determined by isolation and NMR. It was evident from this investigation that the distribution of 2.2 within individual B. leachii specimens was found to be highest within the B. leachii ink gland. The lower amounts of 2.2 contained in the digestive system, relative to other organs, was hypothesized to occur because 2.2 is sequestered from the diet of the sea hare and efficiently moved from the gut to various organs around the body where it is stored. The absence of 2.2 from the skin was surprising and may be a result of a smaller mass of skin relative to other organs coupled with the limitations of the chromatographic separation techniques employed. Surprisingly, no bursatellin was found within juvenile sea hares. Chapter three discusses the isolation of ilimaquinone (3.1) and pelorol (3.19) from the sponge Hippospongia metachroma and the structure elucidation of each compound using computer modeling to illustrate the conformation. It was deemed necessary to isolate these well known and abundant bioactive marine natural products from a sponge as standard compounds in the bioassays given the paucity of 2.2 available for this study. Chapter four describes the assays used to test the biological activity of the bursatellin 2.2 compared to the generally bioactive ilimaquinone and the structurally related and commercially available broad spectrum antibiotic chloramphenicol. B. leachii, a shell-less marine mollusc inhabits a variety of intertidal habitats and, therefore, is exposed to several different predators, yet does not appear to have any specific predators. Potential predators of this sea hare in the Kariega Estuary could be fish and amphipods which are found in close proximity to these sea hares. Results of the assays showed that at roughly natural concentrations, (calculated from the isolated chromatographic yield) feeding was deterred by the fish and amphipods, which implied that 2.2 may confer a defensive role within the organism. The relatively high concentration present within the ink gland of B. leachii may support this hypothesis. Surprisingly, given its structural similarity to chloramphenicol, 2.3 did not show any antimicrobial action against five of the six bacterial strains against which it was screened [chloramphenicol inhibited the growth of all the bacterial strains at very low concentrations (0.25 mg/mL)]. Bursatellin was found to be only active against Staphylococus aureus at high concentrations ca. 2 mg/mL when compared to chloramphenicol. Neither bursatellin nor chloramphenicol showed anti-fungal activity. Although this study suggests that the sea hares may use chemical defences in addition to opaline ink to defend themselves, they also live within the seagrass Z. capensis, which possibly provides the sea hare with a cryptic form of physical defence against several predators that are unable to swim freely within the weed beds in the littoral zone of the estuary. , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
- Authors: D'Souza, Nicole
- Date: 2013 , 2013-03-22
- Subjects: Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4283 , http://hdl.handle.net/10962/d1002952 , Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Description: The large cosmopolitan sea hare Bursatella leachii is a common resident in Eastern Cape river mouths during summer and late autumn where they congregate in beds of Zostera capensis to breed. In this thesis, the previously known toxic formamide marine secondary metabolite (-)-bursatellin (2.2), which may deter predators of South African specimens of the globally distributed sea hare Bursatella leachii, was isolated and identified (Chapter 2). There have been no previous chemical ecology studies of B. leachii and the latter half of this thesis is devoted to chemical ecology studies of this organism. Interestingly, the isolation of the (-)-diastereomer of 2.2 from specimens of B. leachii collected from the Kariega River mouth (near Kenton-on-Sea) suggests that the South African specimens of this species are similar to specimens collected from Puerto Rico and from the Mediterranean Sea. Two different chromatographic techniques for isolating 2.2 were compared in order to maximize the amount of 2.2 isolated from the Kariega River mouth sea hares. The doubling of selected resonances observed in both the ¹H and ¹³C NMR spectra of the bursatellin isolated in this study suggest one of three possibilities; either firstly, the presence of closely related compound(s), secondly, the presence of diastereomers or thirdly the presence of rotamers. Through NMR kinetic studies, we were able to establish that the presence of rotamers was very unlikely due to no change in the relative ratio (3:1) of the ¹H NMR signals with an increase in temperature. Although the attempted synthesis of the acetate derivative (2.28), as a means of separating a diastereomeric mixture was successful, the chromatographic separation of the proposed acetylated diastereomers was not successful. Preparation of the camphanate ester derivatives (e.g. 2.30) proved to be unsuccessful. Five B. leachii specimens were dissected, their organs separated and individually extracted with methanol. The methanol extracts were individually chromatographed on HP-20 media, and the distribution of bursatellin determined by isolation and NMR. It was evident from this investigation that the distribution of 2.2 within individual B. leachii specimens was found to be highest within the B. leachii ink gland. The lower amounts of 2.2 contained in the digestive system, relative to other organs, was hypothesized to occur because 2.2 is sequestered from the diet of the sea hare and efficiently moved from the gut to various organs around the body where it is stored. The absence of 2.2 from the skin was surprising and may be a result of a smaller mass of skin relative to other organs coupled with the limitations of the chromatographic separation techniques employed. Surprisingly, no bursatellin was found within juvenile sea hares. Chapter three discusses the isolation of ilimaquinone (3.1) and pelorol (3.19) from the sponge Hippospongia metachroma and the structure elucidation of each compound using computer modeling to illustrate the conformation. It was deemed necessary to isolate these well known and abundant bioactive marine natural products from a sponge as standard compounds in the bioassays given the paucity of 2.2 available for this study. Chapter four describes the assays used to test the biological activity of the bursatellin 2.2 compared to the generally bioactive ilimaquinone and the structurally related and commercially available broad spectrum antibiotic chloramphenicol. B. leachii, a shell-less marine mollusc inhabits a variety of intertidal habitats and, therefore, is exposed to several different predators, yet does not appear to have any specific predators. Potential predators of this sea hare in the Kariega Estuary could be fish and amphipods which are found in close proximity to these sea hares. Results of the assays showed that at roughly natural concentrations, (calculated from the isolated chromatographic yield) feeding was deterred by the fish and amphipods, which implied that 2.2 may confer a defensive role within the organism. The relatively high concentration present within the ink gland of B. leachii may support this hypothesis. Surprisingly, given its structural similarity to chloramphenicol, 2.3 did not show any antimicrobial action against five of the six bacterial strains against which it was screened [chloramphenicol inhibited the growth of all the bacterial strains at very low concentrations (0.25 mg/mL)]. Bursatellin was found to be only active against Staphylococus aureus at high concentrations ca. 2 mg/mL when compared to chloramphenicol. Neither bursatellin nor chloramphenicol showed anti-fungal activity. Although this study suggests that the sea hares may use chemical defences in addition to opaline ink to defend themselves, they also live within the seagrass Z. capensis, which possibly provides the sea hare with a cryptic form of physical defence against several predators that are unable to swim freely within the weed beds in the littoral zone of the estuary. , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
Fixed points of single-valued and multi-valued mappings with applications
- Authors: Stofile, Simfumene
- Date: 2013
- Subjects: Fixed point theory Mappings (Mathematics) Coincidence theory (Mathematics) Metric spaces Uniform spaces Set-valued maps
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5397 , http://hdl.handle.net/10962/d1002960
- Description: The relationship between the convergence of a sequence of self mappings of a metric space and their fixed points, known as the stability (or continuity) of fixed points has been of continuing interest and widely studied in fixed point theory. In this thesis we study the stability of common fixed points in a Hausdorff uniform space whose uniformity is generated by a family of pseudometrics, by using some general notations of convergence. These results are then extended to 2-metric spaces due to S. Gähler. In addition, a well-known theorem of T. Suzuki that generalized the Banach Contraction Principle is also extended to 2-metric spaces and applied to obtain a coincidence theorem for a pair of mappings on an arbitrary set with values in a 2-metric space. Further, we prove the existence of coincidence and fixed points of Ćirić type weakly generalized contractions in metric spaces. Subsequently, the above result is utilized to discuss applications to the convergence of modified Mann and Ishikawa iterations in a convex metric space. Finally, we obtain coincidence, fixed and stationary point results for multi-valued and hybrid pairs of mappings on a metric space.
- Full Text:
- Date Issued: 2013
- Authors: Stofile, Simfumene
- Date: 2013
- Subjects: Fixed point theory Mappings (Mathematics) Coincidence theory (Mathematics) Metric spaces Uniform spaces Set-valued maps
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5397 , http://hdl.handle.net/10962/d1002960
- Description: The relationship between the convergence of a sequence of self mappings of a metric space and their fixed points, known as the stability (or continuity) of fixed points has been of continuing interest and widely studied in fixed point theory. In this thesis we study the stability of common fixed points in a Hausdorff uniform space whose uniformity is generated by a family of pseudometrics, by using some general notations of convergence. These results are then extended to 2-metric spaces due to S. Gähler. In addition, a well-known theorem of T. Suzuki that generalized the Banach Contraction Principle is also extended to 2-metric spaces and applied to obtain a coincidence theorem for a pair of mappings on an arbitrary set with values in a 2-metric space. Further, we prove the existence of coincidence and fixed points of Ćirić type weakly generalized contractions in metric spaces. Subsequently, the above result is utilized to discuss applications to the convergence of modified Mann and Ishikawa iterations in a convex metric space. Finally, we obtain coincidence, fixed and stationary point results for multi-valued and hybrid pairs of mappings on a metric space.
- Full Text:
- Date Issued: 2013
Falcipains as malarial drug targets
- Authors: Kanzi, Aquillah Mumo
- Date: 2013
- Subjects: Malaria Malaria -- Chemotherapy Plasmodium falciparum Antimalarials -- Development Cysteine proteinases Cysteine proteinases -- Inhibitors Papain Drug development Bioinformatics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3897 , http://hdl.handle.net/10962/d1003842
- Description: Malaria is an infectious disease caused by parasites of the Plasmodium genus with mortality rates of more than a million annually, hence a major global public health concern. Plasmodium falciparum (P. falciparum) accounts for over 90% of malaria incidence. Increased resistance to antimalarial drugs by the Plasmodium parasite, coupled with the lack of an effective malaria vaccine necessitates the urgent need for new research avenues to develop novel and more potent antimalarial drugs. This study focused on falcipains, a group of P. falciparum cysteine proteases that belong to the clan CA and papain family C1, that have emerged as potential drug targets due to their involvement in a range of crucial functions in the P. falciparum life cycle. Recently, falcipain-2 has been validated as a drug target but little is known of its Plasmodium orthologs. Currently, there are several falcipain inhibitors that have been identified, most of which are peptide based but none has proceeded to drug development due to associated poor pharmacological profiles and susceptibility to degradation by host cysteine proteases. Non-peptides inhibitors have been shown to be more stable in vivo but limited information exists. In vivo studies on falcipain-2 and falcipain-3 inhibitors have also been complicated by varying outcomes, thus a good understanding of the structural variations of falcipain Plasmodium orthologs at the active site could go a long way to ease in vivo results interpretation and effective inhibitor design. In this study, we use bioinformatics approaches to perform comparative sequence and structural analysis and molecular docking to characterize protein-inhibitor interactions of falcipain homologs at the active site. Known FP-2 and FP-3 small molecule nonpeptide inhibitors were used to identify residue variations and their effect on inhibitor binding. This was done with the aim of screening a collection of selected non-peptide compounds of South African natural origin to identify possible new inhibitor leads. Natural compounds with high binding affinities across all Plasmodium orthologs were identified. These compounds were then used to search the ZINC database for similar compounds which could have better binding affinities across all selected falcipain homologs. Compounds with high binding affinities across all Plasmodium orthologs were found.
- Full Text:
- Date Issued: 2013
- Authors: Kanzi, Aquillah Mumo
- Date: 2013
- Subjects: Malaria Malaria -- Chemotherapy Plasmodium falciparum Antimalarials -- Development Cysteine proteinases Cysteine proteinases -- Inhibitors Papain Drug development Bioinformatics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3897 , http://hdl.handle.net/10962/d1003842
- Description: Malaria is an infectious disease caused by parasites of the Plasmodium genus with mortality rates of more than a million annually, hence a major global public health concern. Plasmodium falciparum (P. falciparum) accounts for over 90% of malaria incidence. Increased resistance to antimalarial drugs by the Plasmodium parasite, coupled with the lack of an effective malaria vaccine necessitates the urgent need for new research avenues to develop novel and more potent antimalarial drugs. This study focused on falcipains, a group of P. falciparum cysteine proteases that belong to the clan CA and papain family C1, that have emerged as potential drug targets due to their involvement in a range of crucial functions in the P. falciparum life cycle. Recently, falcipain-2 has been validated as a drug target but little is known of its Plasmodium orthologs. Currently, there are several falcipain inhibitors that have been identified, most of which are peptide based but none has proceeded to drug development due to associated poor pharmacological profiles and susceptibility to degradation by host cysteine proteases. Non-peptides inhibitors have been shown to be more stable in vivo but limited information exists. In vivo studies on falcipain-2 and falcipain-3 inhibitors have also been complicated by varying outcomes, thus a good understanding of the structural variations of falcipain Plasmodium orthologs at the active site could go a long way to ease in vivo results interpretation and effective inhibitor design. In this study, we use bioinformatics approaches to perform comparative sequence and structural analysis and molecular docking to characterize protein-inhibitor interactions of falcipain homologs at the active site. Known FP-2 and FP-3 small molecule nonpeptide inhibitors were used to identify residue variations and their effect on inhibitor binding. This was done with the aim of screening a collection of selected non-peptide compounds of South African natural origin to identify possible new inhibitor leads. Natural compounds with high binding affinities across all Plasmodium orthologs were identified. These compounds were then used to search the ZINC database for similar compounds which could have better binding affinities across all selected falcipain homologs. Compounds with high binding affinities across all Plasmodium orthologs were found.
- Full Text:
- Date Issued: 2013
Mg/Triethylammonium Formate: A Useful System for Reductive Dimerization of Araldehydes into Pinacols;Nitroarenes into Azoarenes and Azoarenes into Hydrazoarenes
- Pamar, M Geeter, Govender, P, Muthusamy, K, Krause, Rui W M
- Authors: Pamar, M Geeter , Govender, P , Muthusamy, K , Krause, Rui W M
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125107 , vital:35729 , https://doi.org/10.13005/ojc/290316
- Description: Studies are reported which describes the effectiveness of triethylammonium formate in the presence of magnesium for the efficient intermolecular pinacol coupling using MeOH as solvent. Various aromatic carbonyls underwent smooth reductive coupling to give the corresponding 1,2-diols. A series of azo compounds were obtained by the reductive coupling of nitroaromatics while azo compounds were reduced to the corresponding hydrazoarenes by this system. There was no adverse effect on the other reducible and hydrogenolysable groups such as ether linkage, hydroxy and halogens. The reactions are clean, high yielding and inexpensive. All the reactions proceeded smoothly at ambient temperature.
- Full Text:
- Date Issued: 2013
- Authors: Pamar, M Geeter , Govender, P , Muthusamy, K , Krause, Rui W M
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/125107 , vital:35729 , https://doi.org/10.13005/ojc/290316
- Description: Studies are reported which describes the effectiveness of triethylammonium formate in the presence of magnesium for the efficient intermolecular pinacol coupling using MeOH as solvent. Various aromatic carbonyls underwent smooth reductive coupling to give the corresponding 1,2-diols. A series of azo compounds were obtained by the reductive coupling of nitroaromatics while azo compounds were reduced to the corresponding hydrazoarenes by this system. There was no adverse effect on the other reducible and hydrogenolysable groups such as ether linkage, hydroxy and halogens. The reactions are clean, high yielding and inexpensive. All the reactions proceeded smoothly at ambient temperature.
- Full Text:
- Date Issued: 2013