Detecting impacts of invasive non-native sharptooth catfish, Clarias gariepinus, within invaded and non-invaded rivers.
- Kadye, Wilbert T, Booth, Anthony J
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124100 , vital:35539 , https://doi.10.1007/s10531-012-0291-5
- Description: In aquatic ecosystems, impacts by invasive introduced fish can be likened to press disturbances that persistently influence communities. This study examined invasion disturbances by determining the relationship between non-native sharptooth catfish Clarias gariepinus and aquatic macroinvertebrates in the Eastern Cape, South Africa. A Multiple Before–After Control–Impact (MBACI) experimental design was used to examine macroinvertebrate communities within two rivers: one with catfish and another one without catfish. Within the invaded river, macroinvertebrates showed little response to catfish presence, whereas predator exclusion appeared to benefit community structure. This suggests that the macroinvertebrate community within the invaded river was adapted to predation impact because of the dominance of resilient taxa, such as Hirudinea, Oligochaeta and Chironomidae that were abundant in the Impact treatment relative to the Control treatment. High macroinvertebrate diversity and richness that was observed in the Control treatment, which excluded the predator, relative to the Impact treatment suggests predator avoidance behaviour within the invaded river. By comparison, within the uninvaded river, catfish introduction into the Impact treatment plots indicated negative effects on macroinvertebrate community that was reflected by decrease in diversity, richness and biomass. A community level impact was also reflected in the multivariate analysis that indicated more variation in macroinvertebrate composition within the Impact treatment relative to the Control in the uninvaded river. Catfish impact within the uninvaded river suggests the dominance of vulnerable taxa, such as odonates that were less abundant in the Impact treatment plots after catfish introduction. From a disturbance perspective, this study revealed different macroinvertebrate responses to catfish impact, and suggests that within invaded habitats, macroinvertebrates were less responsive to catfish presence, whereas catfish introduction within uninvaded habitats demonstrated invasion impact that was shown by a decrease in the abundance of vulnerable taxa. The occurrence of non-native sharptooth catfish within many Eastern Cape rivers is a concern because of its predation impact and potential to influence trophic interrelationships, and efforts should be taken to protect uninvaded rivers, and, where possible, eradicate the invader.
- Full Text:
- Date Issued: 2012
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124100 , vital:35539 , https://doi.10.1007/s10531-012-0291-5
- Description: In aquatic ecosystems, impacts by invasive introduced fish can be likened to press disturbances that persistently influence communities. This study examined invasion disturbances by determining the relationship between non-native sharptooth catfish Clarias gariepinus and aquatic macroinvertebrates in the Eastern Cape, South Africa. A Multiple Before–After Control–Impact (MBACI) experimental design was used to examine macroinvertebrate communities within two rivers: one with catfish and another one without catfish. Within the invaded river, macroinvertebrates showed little response to catfish presence, whereas predator exclusion appeared to benefit community structure. This suggests that the macroinvertebrate community within the invaded river was adapted to predation impact because of the dominance of resilient taxa, such as Hirudinea, Oligochaeta and Chironomidae that were abundant in the Impact treatment relative to the Control treatment. High macroinvertebrate diversity and richness that was observed in the Control treatment, which excluded the predator, relative to the Impact treatment suggests predator avoidance behaviour within the invaded river. By comparison, within the uninvaded river, catfish introduction into the Impact treatment plots indicated negative effects on macroinvertebrate community that was reflected by decrease in diversity, richness and biomass. A community level impact was also reflected in the multivariate analysis that indicated more variation in macroinvertebrate composition within the Impact treatment relative to the Control in the uninvaded river. Catfish impact within the uninvaded river suggests the dominance of vulnerable taxa, such as odonates that were less abundant in the Impact treatment plots after catfish introduction. From a disturbance perspective, this study revealed different macroinvertebrate responses to catfish impact, and suggests that within invaded habitats, macroinvertebrates were less responsive to catfish presence, whereas catfish introduction within uninvaded habitats demonstrated invasion impact that was shown by a decrease in the abundance of vulnerable taxa. The occurrence of non-native sharptooth catfish within many Eastern Cape rivers is a concern because of its predation impact and potential to influence trophic interrelationships, and efforts should be taken to protect uninvaded rivers, and, where possible, eradicate the invader.
- Full Text:
- Date Issued: 2012
Inter-seasonal persistence and size-structuring of two minnow species within headwater streams in the Eastern Cape, South Africa
- Kadye, Wilbert T, Booth, Anthony J
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124866 , vital:35705 , https://doi.10.1111/j.1439-0426.2012.02027.x
- Description: This study examined temporal variation in population dynamics and size structuring of two cyprinid minnows, Pseudobarbus afer and Barbus anoplus, in relation to their proximate physical habitats. Population estimates were determined using three-pass depletion sampling during both summer and winter. The habitats were characterised by seasonal variation in all physico-chemical conditions and spatial variation in substrata compositions. Whereas significant differences in population size were noted between seasons for B. anoplus, no differences were found between seasons for density and capture probability for either species. An increase in boulders was associated with increase in population size and density for P. afer; for B. anoplus, increased percentages of bedrock and bank vegetation were associated with an increase in population size and probability of capture, respectively. According to Canonical Correspondence Analysis, size structuring in P. afer was explained predominantly by seasonality, with smaller length classes associated with the seasonal variable of summer, while larger length classes were associated with pH that was higher in winter. By comparison, for B. anoplus, the habitat variables – bank vegetation and bedrock – accounted for much of the explained variance for size structuring. Recruitment appeared to be the major driver of size structuring for the two species; refugia, especially boulders and bank vegetation, also appeared to be important. Overall, the two species were adapted to the headwater streams that were generally variable in environmental conditions. Potential invasions by non-native invasive fishes that occur within the mainstream habitats threaten these two species. Efforts should continue to protect these minnows from such invasions by constructing barriers to upstream migration of non-native fishes into these headwater habitats.
- Full Text:
- Date Issued: 2012
- Authors: Kadye, Wilbert T , Booth, Anthony J
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/124866 , vital:35705 , https://doi.10.1111/j.1439-0426.2012.02027.x
- Description: This study examined temporal variation in population dynamics and size structuring of two cyprinid minnows, Pseudobarbus afer and Barbus anoplus, in relation to their proximate physical habitats. Population estimates were determined using three-pass depletion sampling during both summer and winter. The habitats were characterised by seasonal variation in all physico-chemical conditions and spatial variation in substrata compositions. Whereas significant differences in population size were noted between seasons for B. anoplus, no differences were found between seasons for density and capture probability for either species. An increase in boulders was associated with increase in population size and density for P. afer; for B. anoplus, increased percentages of bedrock and bank vegetation were associated with an increase in population size and probability of capture, respectively. According to Canonical Correspondence Analysis, size structuring in P. afer was explained predominantly by seasonality, with smaller length classes associated with the seasonal variable of summer, while larger length classes were associated with pH that was higher in winter. By comparison, for B. anoplus, the habitat variables – bank vegetation and bedrock – accounted for much of the explained variance for size structuring. Recruitment appeared to be the major driver of size structuring for the two species; refugia, especially boulders and bank vegetation, also appeared to be important. Overall, the two species were adapted to the headwater streams that were generally variable in environmental conditions. Potential invasions by non-native invasive fishes that occur within the mainstream habitats threaten these two species. Efforts should continue to protect these minnows from such invasions by constructing barriers to upstream migration of non-native fishes into these headwater habitats.
- Full Text:
- Date Issued: 2012
The genetic integrity of Labeo capensis and L. umbratus (Cyprinidae) in South Africa in relation to inter-basin water transfer schemes
- Authors: Ramoejane, Mpho
- Date: 2011
- Subjects: Cyprinidae -- South Africa -- Darlington Dam , Cyprinidae -- Namibia -- Hardap Dam , Labeo -- South Africa -- Darlington Dam , Labeo -- Namibia -- Hardap Dam , Fishes -- Hybridisation -- South Africa -- Darlington Dam , Fishes -- Hybridisation -- Namibia -- Hardap Dam , Fishes -- Anatomy -- South Africa -- Darlington Dam , Fishes -- Anatomy -- Namibia -- Hardap Dam , Water transfer -- South Africa-- Darlington Dam , Water transfer -- Namibia -- Hardap Dam
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5367 , http://hdl.handle.net/10962/d1013049
- Description: The Orange-Fish and Cookhouse tunnels that are part of a major inter-basin water transfer scheme (IBT) act as a pathway for several fish species from the Orange River system to enter the Great Fish and Sundays River systems in South Africa. These include Labeo capensis and L. umbratus. Labeo capensis was restricted to the Orange River system before the inter-basin water transfer scheme. Labeo umbratus occurred naturally in the Orange River and in southern flowing river systems. Previous studies showed that the two species hybridise in Hardap Dam, located in a tributary of the Orange River system in Namibia. There are also unconfirmed reports of hybrids from Darlington Dam on the Sundays River system. The aim of the thesis was to confirm hybridisation in Hardap Dam, assess whether hybridisation between L. capensis and L. umbratus has occurred in Darlington Dam and to gain a better understanding of the diversity of these two species. Morphology (morphometrics and meristics), a nuclear S7 intron and the mitochondrial cytochrome ♭ gene were used to assess for hybridisation. A total of 275 specimens were analysed from across the geographical range of the two species. The two species could be distinguished using morphometrics (dorsal fin base, interorbital width and operculum to eye distance) and meristics (lateral line, origin of the dorsal fin to lateral line, origin of the pelvic fin to lateral line and caudal peduncle scale counts) characters. Hybrids from Hardap and Darlington dams were placed between the two species clusters. Labeo umbratus from the Orange River and southern flowing rivers formed a single cluster. The two species could also be distinguished from each other with six nuclear DNA mutations and hybrids were heterozygous at such sites in both dams. Labeo umbratus populations from the Orange River and southern flowing rivers (Gouritz, Gamtoos, Sundays, Bushmans, Great Fish and Nahoon) formed a single lineage. Analysis of mitochondrial DNA, however, revealed that L. umbratus populations from the Orange River and southern flowing rivers were two lineages that differ from each other by 5 mutations. Labeo capensis could be differentiated from both these lineages. Being maternally inherited, mitochondrial DNA did not reveal hybridisation, but ten specimens with L. capensis haplotypes were found in the Darlington Dam. In Hardap Dam, however, it appears that only L. capensis mitochondrial DNA haplotypes persist, despite morphological and nuclear DNA analysis suggesting that both morphs and hybrids of the two species occur. The genetic integrity of these Labeo species has therefore been compromised in at least Hardap and Darlington dams. The Great Fish and Sundays populations are considered to be under threat of complete introgression. The Kat River and Slagboom Dam populations that were isolated before the IBTs have to remain isolated to protect the genetic integrity of the southern lineage of L. umbratus in these two systems.
- Full Text:
- Date Issued: 2011
- Authors: Ramoejane, Mpho
- Date: 2011
- Subjects: Cyprinidae -- South Africa -- Darlington Dam , Cyprinidae -- Namibia -- Hardap Dam , Labeo -- South Africa -- Darlington Dam , Labeo -- Namibia -- Hardap Dam , Fishes -- Hybridisation -- South Africa -- Darlington Dam , Fishes -- Hybridisation -- Namibia -- Hardap Dam , Fishes -- Anatomy -- South Africa -- Darlington Dam , Fishes -- Anatomy -- Namibia -- Hardap Dam , Water transfer -- South Africa-- Darlington Dam , Water transfer -- Namibia -- Hardap Dam
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5367 , http://hdl.handle.net/10962/d1013049
- Description: The Orange-Fish and Cookhouse tunnels that are part of a major inter-basin water transfer scheme (IBT) act as a pathway for several fish species from the Orange River system to enter the Great Fish and Sundays River systems in South Africa. These include Labeo capensis and L. umbratus. Labeo capensis was restricted to the Orange River system before the inter-basin water transfer scheme. Labeo umbratus occurred naturally in the Orange River and in southern flowing river systems. Previous studies showed that the two species hybridise in Hardap Dam, located in a tributary of the Orange River system in Namibia. There are also unconfirmed reports of hybrids from Darlington Dam on the Sundays River system. The aim of the thesis was to confirm hybridisation in Hardap Dam, assess whether hybridisation between L. capensis and L. umbratus has occurred in Darlington Dam and to gain a better understanding of the diversity of these two species. Morphology (morphometrics and meristics), a nuclear S7 intron and the mitochondrial cytochrome ♭ gene were used to assess for hybridisation. A total of 275 specimens were analysed from across the geographical range of the two species. The two species could be distinguished using morphometrics (dorsal fin base, interorbital width and operculum to eye distance) and meristics (lateral line, origin of the dorsal fin to lateral line, origin of the pelvic fin to lateral line and caudal peduncle scale counts) characters. Hybrids from Hardap and Darlington dams were placed between the two species clusters. Labeo umbratus from the Orange River and southern flowing rivers formed a single cluster. The two species could also be distinguished from each other with six nuclear DNA mutations and hybrids were heterozygous at such sites in both dams. Labeo umbratus populations from the Orange River and southern flowing rivers (Gouritz, Gamtoos, Sundays, Bushmans, Great Fish and Nahoon) formed a single lineage. Analysis of mitochondrial DNA, however, revealed that L. umbratus populations from the Orange River and southern flowing rivers were two lineages that differ from each other by 5 mutations. Labeo capensis could be differentiated from both these lineages. Being maternally inherited, mitochondrial DNA did not reveal hybridisation, but ten specimens with L. capensis haplotypes were found in the Darlington Dam. In Hardap Dam, however, it appears that only L. capensis mitochondrial DNA haplotypes persist, despite morphological and nuclear DNA analysis suggesting that both morphs and hybrids of the two species occur. The genetic integrity of these Labeo species has therefore been compromised in at least Hardap and Darlington dams. The Great Fish and Sundays populations are considered to be under threat of complete introgression. The Kat River and Slagboom Dam populations that were isolated before the IBTs have to remain isolated to protect the genetic integrity of the southern lineage of L. umbratus in these two systems.
- Full Text:
- Date Issued: 2011
A study of a class of invariant optimal control problems on the Euclidean group SE(2)
- Authors: Adams, Ross Montague
- Date: 2011
- Subjects: Matrix groups Lie groups Extremal problems (Mathematics) Maximum principles (Mathematics) Hamilton-Jacobi equations Lyapunov stability
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5420 , http://hdl.handle.net/10962/d1006060
- Description: The aim of this thesis is to study a class of left-invariant optimal control problems on the matrix Lie group SE(2). We classify, under detached feedback equivalence, all controllable (left-invariant) control affine systems on SE(2). This result produces six types of control affine systems on SE(2). Hence, we study six associated left-invariant optimal control problems on SE(2). A left-invariant optimal control problem consists of minimizing a cost functional over the trajectory-control pairs of a left-invariant control system subject to appropriate boundary conditions. Each control problem is lifted from SE(2) to T*SE(2) ≅ SE(2) x se (2)*and then reduced to a problem on se (2)*. The maximum principle is used to obtain the optimal control and Hamiltonian corresponding to the normal extremals. Then we derive the (reduced) extremal equations on se (2)*. These equations are explicitly integrated by trigonometric and Jacobi elliptic functions. Finally, we fully classify, under Lyapunov stability, the equilibrium states of the normal extremal equations for each of the six types under consideration.
- Full Text:
- Date Issued: 2011
- Authors: Adams, Ross Montague
- Date: 2011
- Subjects: Matrix groups Lie groups Extremal problems (Mathematics) Maximum principles (Mathematics) Hamilton-Jacobi equations Lyapunov stability
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5420 , http://hdl.handle.net/10962/d1006060
- Description: The aim of this thesis is to study a class of left-invariant optimal control problems on the matrix Lie group SE(2). We classify, under detached feedback equivalence, all controllable (left-invariant) control affine systems on SE(2). This result produces six types of control affine systems on SE(2). Hence, we study six associated left-invariant optimal control problems on SE(2). A left-invariant optimal control problem consists of minimizing a cost functional over the trajectory-control pairs of a left-invariant control system subject to appropriate boundary conditions. Each control problem is lifted from SE(2) to T*SE(2) ≅ SE(2) x se (2)*and then reduced to a problem on se (2)*. The maximum principle is used to obtain the optimal control and Hamiltonian corresponding to the normal extremals. Then we derive the (reduced) extremal equations on se (2)*. These equations are explicitly integrated by trigonometric and Jacobi elliptic functions. Finally, we fully classify, under Lyapunov stability, the equilibrium states of the normal extremal equations for each of the six types under consideration.
- Full Text:
- Date Issued: 2011
Structural and functional characterisation of the protein inhibitor of activated STAT3 (PIAS3)
- Authors: Mautsa, Nicodemus
- Date: 2011
- Subjects: Cytokines Immune response Proteins Cancer cells -- Growth -- Regulation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3991 , http://hdl.handle.net/10962/d1004050
- Description: The signal transducer and activator of transcription (STAT) and protein inhibitor of STAT(PIAS) system represent an elegant regulatory mechanism of transcriptional control IN mammalian cytokine signalling. Abnormal activation of the system is associated with immune disorders and a large group of diverse tumours. PIAS3 is a multiple domain protein with distinct functions involved in regulation of cytokine-mediated gene activation pathways.Its over-expression significantly inhibits cell growth and renders cancer cells more sensitive to drugs. The objective of this study was to structurally and biochemically characterise the function of the PIAS3 protein using in silico, in vivo and in vitro analysis approaches.The conservation pattern of the PIAS protein family and critical conserved residues in the PINIT (Proline, Isoleucine, Asparagine, Isoleucine, Tyrosine) domain were identified. The PINIT domain model was generated based on the PINIT domain structure of yeast PIAS3 homologue Siz1 and structural determinants in the PIAS3-STAT3 interaction were evaluated.Guided by the in silico findings, in vivo analysis of the localisation of the PIAS3, mutantderivatives of PIAS3 (PIAS3-L97A, PIAS3-R99N, PIAS3-R99Q), PINIT and acidic domain was conducted. PIAS3 was completely localised in the nucleus while PIAS3 mutants appeared to exhibit diffuse cytoplasmic distribution. The PINIT domain was predominantly localised in the nucleus with some apparent perinuclear staining while the acidic domain exhibited a predominantly perinuclear staining pattern. Further analysis of the PINIT domain and the effect of the mutants on PIAS3-STAT3 interaction were assessed by in vitro analysis. Guided by in silico analysis, the PINIT domain and mutant derivatives of PINIT domain (PINIT-L97A, PINIT-R99N, and PINIT-R99Q) were heterologously expressed in Escherichia coli and subsequently purified using a combination of immobilized metal affinity and size exclusion based chromatography. The size and structural elements of the PINIT domain and its mutants were characterised. The 23 kDa PINIT domain was found to exist as a monomer in solution and its secondary structure was shown to consist of 66 % β-sheets by fourier transformed infrared spectroscopy consistent with the generated homology model.Using surface plasmonresonance spectroscopy (SPR) the PINIT domain was shown to bind to STAT3 in a specific concentration dependent manner. Recombinant PINIT-L97A,PINITR99N and PINIT-R99Q mutants, which exhibited similar structural integrity to the wildtype, were found to abrogate binding to STAT3. These findings suggest that these residues form part of a potential binding surface for stat3. In conclusion, this study has provided evidence that the PINIT domain is an important determinant of PIAS3 interaction with STAT3 and that the interaction is mediated by defined conserved residues directly involved in the PINITSTAT3 interaction.
- Full Text:
- Date Issued: 2011
- Authors: Mautsa, Nicodemus
- Date: 2011
- Subjects: Cytokines Immune response Proteins Cancer cells -- Growth -- Regulation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3991 , http://hdl.handle.net/10962/d1004050
- Description: The signal transducer and activator of transcription (STAT) and protein inhibitor of STAT(PIAS) system represent an elegant regulatory mechanism of transcriptional control IN mammalian cytokine signalling. Abnormal activation of the system is associated with immune disorders and a large group of diverse tumours. PIAS3 is a multiple domain protein with distinct functions involved in regulation of cytokine-mediated gene activation pathways.Its over-expression significantly inhibits cell growth and renders cancer cells more sensitive to drugs. The objective of this study was to structurally and biochemically characterise the function of the PIAS3 protein using in silico, in vivo and in vitro analysis approaches.The conservation pattern of the PIAS protein family and critical conserved residues in the PINIT (Proline, Isoleucine, Asparagine, Isoleucine, Tyrosine) domain were identified. The PINIT domain model was generated based on the PINIT domain structure of yeast PIAS3 homologue Siz1 and structural determinants in the PIAS3-STAT3 interaction were evaluated.Guided by the in silico findings, in vivo analysis of the localisation of the PIAS3, mutantderivatives of PIAS3 (PIAS3-L97A, PIAS3-R99N, PIAS3-R99Q), PINIT and acidic domain was conducted. PIAS3 was completely localised in the nucleus while PIAS3 mutants appeared to exhibit diffuse cytoplasmic distribution. The PINIT domain was predominantly localised in the nucleus with some apparent perinuclear staining while the acidic domain exhibited a predominantly perinuclear staining pattern. Further analysis of the PINIT domain and the effect of the mutants on PIAS3-STAT3 interaction were assessed by in vitro analysis. Guided by in silico analysis, the PINIT domain and mutant derivatives of PINIT domain (PINIT-L97A, PINIT-R99N, and PINIT-R99Q) were heterologously expressed in Escherichia coli and subsequently purified using a combination of immobilized metal affinity and size exclusion based chromatography. The size and structural elements of the PINIT domain and its mutants were characterised. The 23 kDa PINIT domain was found to exist as a monomer in solution and its secondary structure was shown to consist of 66 % β-sheets by fourier transformed infrared spectroscopy consistent with the generated homology model.Using surface plasmonresonance spectroscopy (SPR) the PINIT domain was shown to bind to STAT3 in a specific concentration dependent manner. Recombinant PINIT-L97A,PINITR99N and PINIT-R99Q mutants, which exhibited similar structural integrity to the wildtype, were found to abrogate binding to STAT3. These findings suggest that these residues form part of a potential binding surface for stat3. In conclusion, this study has provided evidence that the PINIT domain is an important determinant of PIAS3 interaction with STAT3 and that the interaction is mediated by defined conserved residues directly involved in the PINITSTAT3 interaction.
- Full Text:
- Date Issued: 2011
Ericoid mycorrhizal fungi and potential for inoculation of commercial berry species (Vaccinium corymbosium L.)
- Authors: Bizabani, Christine
- Date: 2011
- Subjects: Ericaceae , Mycorrhizas , Fynbos
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4136 , http://hdl.handle.net/10962/d1016127
- Description: Ericaceous plants are the richest growth form of the fynbos vegetation of South Africa. The fynbos is characterized by highly leached acidic soils, low mineral nutrients and climatically it is a winter rainfall and dry summer region. Ericoid mycorrhizal fungi associate with Erica species enhancing their ability to access essential nutrients for survival under unfavourable growth conditions. The aim of this study was to select local Ericaceae plant species and to isolate, identify and characterize the ericoid endophytes and assess these isolates as potential inocula for commercial berry species. Two ericaceous plants Erica cerinthoides L. and Erica demmissa Klotzsch ex Benth. were identified from the Mountain Drive area of Grahamstown, Eastern Cape. Root staining was used to confirm the mycorrhizal status of both plants. Hyphal coils typical of ericoid association were observed within the epidermal cells of the hair roots under a light microscope. The endophytes were successfully isolated in pure culture on 2% malt extract agar (MEA) and modified Fontana medium. Cultural morphology and microscopy were used for initial identification. Two slow growing isolates were selected. These isolates were further subjected to molecular identification; extracted DNA was amplified using ITS1 and ITS4 fungal primers. The rDNA gene internal transcriber spacer (ITS) was then sequenced and analyzed by comparison to sequences in the GenBank. On the basis of percentage sequence identity Lachnum Retz. species and Cadophora Lagerb. & Melin species were identified as the ericoid endophytes of E. cerinthoides and E. demmissa respectively. The optimum growth parameters of the fungal isolates were determined in 2% MEA incubated at varying temperatures and pH. It was established that both species had optimum growth at 27⁰C and pH 5. The Ericaceae species are sometimes found in metal contaminated sites were ericoid fungi have been proved to alleviate toxicity of their host. The fungal isolates were grown in increasing concentration of Cu²⁺ and Zn²⁺ in 2% MEA. The growth of Lachnum species decreased with increasing Zn²⁺ ions above 2.7 mM while Cadophora species showed a change in morphology and also decreased in growth with increased ion concentration. However there were no significant differences recorded in the growth of Cadophora and Lachnum species on increasing Cu²⁺ concentration. Lachnum and Cadophora isolates were formulated into a semi solid inoculum and inoculated onto micropropagated Vaccinni corymbosum L. plantlets of 5 different varieties. Colonization was low for all varieties, Elliott and Brightwell varieties recorded the highest colonization of 35% and 31% respectively. Lachnum species infected roots showed potential ericoid structures while the Cadophora inoculated plantlets had hyphal coils within the cortical cells typical of ericoid mycorrhizas. Inoculation significantly enhanced the shoot growth of Brightwell and Elliott varieties. The Chandler variety inoculated with Lachnum species showed improved shoot dry weight. The Bluecrop and Elliott varieties inoculated with Cadophora and Lachnum accumulated more root biomass. All inoculated Bluecrop plantlets had an improved canopy growth index. Brightwell plantlets inoculated with Lachnum species also had an enhanced canopy growth index. The growth responses were variable within varieties and between varieties. Treatments with the Cadophora and Lachnum have shown potential in the promotion of growth of the Blueberry species. The findings indicate the need to conduct trials under conditions which simulate the commercial growth conditions so as explore the optimum potential of the isolates.
- Full Text:
- Date Issued: 2011
- Authors: Bizabani, Christine
- Date: 2011
- Subjects: Ericaceae , Mycorrhizas , Fynbos
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4136 , http://hdl.handle.net/10962/d1016127
- Description: Ericaceous plants are the richest growth form of the fynbos vegetation of South Africa. The fynbos is characterized by highly leached acidic soils, low mineral nutrients and climatically it is a winter rainfall and dry summer region. Ericoid mycorrhizal fungi associate with Erica species enhancing their ability to access essential nutrients for survival under unfavourable growth conditions. The aim of this study was to select local Ericaceae plant species and to isolate, identify and characterize the ericoid endophytes and assess these isolates as potential inocula for commercial berry species. Two ericaceous plants Erica cerinthoides L. and Erica demmissa Klotzsch ex Benth. were identified from the Mountain Drive area of Grahamstown, Eastern Cape. Root staining was used to confirm the mycorrhizal status of both plants. Hyphal coils typical of ericoid association were observed within the epidermal cells of the hair roots under a light microscope. The endophytes were successfully isolated in pure culture on 2% malt extract agar (MEA) and modified Fontana medium. Cultural morphology and microscopy were used for initial identification. Two slow growing isolates were selected. These isolates were further subjected to molecular identification; extracted DNA was amplified using ITS1 and ITS4 fungal primers. The rDNA gene internal transcriber spacer (ITS) was then sequenced and analyzed by comparison to sequences in the GenBank. On the basis of percentage sequence identity Lachnum Retz. species and Cadophora Lagerb. & Melin species were identified as the ericoid endophytes of E. cerinthoides and E. demmissa respectively. The optimum growth parameters of the fungal isolates were determined in 2% MEA incubated at varying temperatures and pH. It was established that both species had optimum growth at 27⁰C and pH 5. The Ericaceae species are sometimes found in metal contaminated sites were ericoid fungi have been proved to alleviate toxicity of their host. The fungal isolates were grown in increasing concentration of Cu²⁺ and Zn²⁺ in 2% MEA. The growth of Lachnum species decreased with increasing Zn²⁺ ions above 2.7 mM while Cadophora species showed a change in morphology and also decreased in growth with increased ion concentration. However there were no significant differences recorded in the growth of Cadophora and Lachnum species on increasing Cu²⁺ concentration. Lachnum and Cadophora isolates were formulated into a semi solid inoculum and inoculated onto micropropagated Vaccinni corymbosum L. plantlets of 5 different varieties. Colonization was low for all varieties, Elliott and Brightwell varieties recorded the highest colonization of 35% and 31% respectively. Lachnum species infected roots showed potential ericoid structures while the Cadophora inoculated plantlets had hyphal coils within the cortical cells typical of ericoid mycorrhizas. Inoculation significantly enhanced the shoot growth of Brightwell and Elliott varieties. The Chandler variety inoculated with Lachnum species showed improved shoot dry weight. The Bluecrop and Elliott varieties inoculated with Cadophora and Lachnum accumulated more root biomass. All inoculated Bluecrop plantlets had an improved canopy growth index. Brightwell plantlets inoculated with Lachnum species also had an enhanced canopy growth index. The growth responses were variable within varieties and between varieties. Treatments with the Cadophora and Lachnum have shown potential in the promotion of growth of the Blueberry species. The findings indicate the need to conduct trials under conditions which simulate the commercial growth conditions so as explore the optimum potential of the isolates.
- Full Text:
- Date Issued: 2011
a pH-metric speciation and anti-diabetic study of oxovanadium (IV) amino acid derivatives
- Authors: Gundhla, Isaac Zvikomborero
- Date: 2011 , 2011-03-15
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4399 , http://hdl.handle.net/10962/d1006691
- Description: Novel oxovanadium(IV) complexes of glycine, ʟ-alanine, 1-methylimidazole-2-carboxylic acid, imidazole-2-caboxylic acid and imidazole-4-carboxylic acid were synthesized and isolated in the solid state. The ligands and complexes were characterized by elemental analysis, melting point, NMR, IR and UV-vis spectroscopy. The IR studies showed that glycine and ʟ-alanine coordinate monodentately through the amine nitrogen whilst the imidazole-carboxylic acid derivatives assume a bidentate chelation. The electronic spectroscopic studies indicate distorted octahedral geometry for the oxovanadium complexes of amino acids and a square pyramidal geometry for oxovanadium(IV) complexes of imidazole carboxylic acid derivatives. The reaction of vanadyl (VO2+) with glycine, ʟ-alanine, imidazole-2-cabrboxylic acid, imidazole-4-carboxylic acid and 1-methylimidazole-2-carboxylic acid was studied in aqueous solution by pH-potentiometry under oxygen and carbon dioxide-free conditions. The data obtained from these titrations were used to calculate the protonation and stability constants. The results showed that all ligands are suitable for bidentate coordination in the formation of monomeric species although the solid state studies of the oxovanadium(IV) complexes of amino acids showed a monodentate coordination. The overall stability constants for the (VIVO)-ʟ-alanine system (log β120 = 18.27(6)), (VIVO)-glycine system (β120 = 17.22(6)), (VIVO)-imidazole-4-carboxyic acid (β120 = 11.38(8)), (VIVO)-imidazole-2-carboxylic acid (β120 = 11.62(6)) and (VIVO)-1-methylimidazole-2-carboxylic acid (β120 = 15.49(9)) were obtained. The calculations for the species distribution in the experimental pH range showed that the neutral bis-coordinated complexes are dominant over the biological pH range. The glucose uptake effect of oxovanadium(IV) complex of ʟ-alanine, imidazole-4-carboxylic acid, imidazole-2-carboxylic acid and 1-methylimidazole-2-carboxylic acid was investigated using 3T3-L1 adipocytes, Chang liver and C2C12 muscle cells at various concentrations. The compounds had significant glucose uptake on Chang liver cells only at a concentration of 0.1-10 μM whilst in the C2C12 muscle and 3T3-L1 cells the compounds showed little to no activity probably due to the lower concentrations employed as a result of the cytotoxicity of these compounds on these two cell lines.
- Full Text:
- Date Issued: 2011
- Authors: Gundhla, Isaac Zvikomborero
- Date: 2011 , 2011-03-15
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4399 , http://hdl.handle.net/10962/d1006691
- Description: Novel oxovanadium(IV) complexes of glycine, ʟ-alanine, 1-methylimidazole-2-carboxylic acid, imidazole-2-caboxylic acid and imidazole-4-carboxylic acid were synthesized and isolated in the solid state. The ligands and complexes were characterized by elemental analysis, melting point, NMR, IR and UV-vis spectroscopy. The IR studies showed that glycine and ʟ-alanine coordinate monodentately through the amine nitrogen whilst the imidazole-carboxylic acid derivatives assume a bidentate chelation. The electronic spectroscopic studies indicate distorted octahedral geometry for the oxovanadium complexes of amino acids and a square pyramidal geometry for oxovanadium(IV) complexes of imidazole carboxylic acid derivatives. The reaction of vanadyl (VO2+) with glycine, ʟ-alanine, imidazole-2-cabrboxylic acid, imidazole-4-carboxylic acid and 1-methylimidazole-2-carboxylic acid was studied in aqueous solution by pH-potentiometry under oxygen and carbon dioxide-free conditions. The data obtained from these titrations were used to calculate the protonation and stability constants. The results showed that all ligands are suitable for bidentate coordination in the formation of monomeric species although the solid state studies of the oxovanadium(IV) complexes of amino acids showed a monodentate coordination. The overall stability constants for the (VIVO)-ʟ-alanine system (log β120 = 18.27(6)), (VIVO)-glycine system (β120 = 17.22(6)), (VIVO)-imidazole-4-carboxyic acid (β120 = 11.38(8)), (VIVO)-imidazole-2-carboxylic acid (β120 = 11.62(6)) and (VIVO)-1-methylimidazole-2-carboxylic acid (β120 = 15.49(9)) were obtained. The calculations for the species distribution in the experimental pH range showed that the neutral bis-coordinated complexes are dominant over the biological pH range. The glucose uptake effect of oxovanadium(IV) complex of ʟ-alanine, imidazole-4-carboxylic acid, imidazole-2-carboxylic acid and 1-methylimidazole-2-carboxylic acid was investigated using 3T3-L1 adipocytes, Chang liver and C2C12 muscle cells at various concentrations. The compounds had significant glucose uptake on Chang liver cells only at a concentration of 0.1-10 μM whilst in the C2C12 muscle and 3T3-L1 cells the compounds showed little to no activity probably due to the lower concentrations employed as a result of the cytotoxicity of these compounds on these two cell lines.
- Full Text:
- Date Issued: 2011
Synthesis and evaluation of novel HIV-1 enzyme inhibitors
- Olomola, Temitope Oloruntoba
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
- Full Text:
- Date Issued: 2011
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
- Full Text:
- Date Issued: 2011
Synthesis of novel inhibitors of 1-Deoxy-D-xylulose-5-phosphate reductoisomerase as potential anti-malarial lead compounds
- Authors: Mutorwa, Marius Kudumo
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Malaria -- Chemotherapy Drug development Lead compounds Phosphonates Phosphonic acids Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4372 , http://hdl.handle.net/10962/d1005037
- Description: This research has focused on the development of novel substrate mimics as potential DXR inhibitors of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), an essential enzyme in the mevalonate-independent pathway for the biosynthesis of isoprenoids in Plasmodium falciparum. DXR mediates the isomerisation and reduction of 1-deoxy-D-xylulose-5-phosphate (DOXP) into 2C-methyl-D-erithrytol 4-phosphate (MEP) and has been validated as an attractive target for the development of novel anti-malarial chemotherapeutic agents. Reaction of various amines with specially prepared 4-phosphonated crotonic acid in the presence of the peptide coupling reagent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), has afforded a series of amido-phosphonate esters in moderate to good yields (48% - 73%) which, using a RuCl₃/CeCl₃/NaIO₄ catalyst system, have been dihydroxylated to furnish the dihydroxy-amido phosphonate ester pro-drugs; subsequent hydrolysis under microwave irradiation has afforded the corresponding phosphonic acids. A second series of potential inhibitors viz., 3-substituted aniline-derived phosphonate esters, their corresponding phosphonic acids and mono-sodium salts, have also been successfully synthesised. In these compounds, the essential functional groups are separated by one, two, three or four methylene groups, Deprotonation of the 3-substituted aniline substrates, followed by reaction with the appropriate ω-chloroalkanoyl chloride produced the ω-chloroamide intermediates, which were subjected to the Michaelis-Arbuzov reaction to afford the diethyl phosphonate esters in moderate to good yields (48% - 74%). Microwave-assisted TMSBrmediated cleavage of the phosphonate esters furnished the phosphonic acids, neutralisation of which afforded the mono-sodium salts. Furan-derived phosphate esters and phosphonic acids have been prepared as conformationally-restricted DOXP analogues. Functionalization at C-5 of the trityl-protected furan was achieved using the Vilsmeier-Haack formylation and Friedel-Crafts acylation reactions and, following de-tritylation, phosphorylation and oximation, using hydroxylamine hydrochloride, the novel oxime derivatives have been isolated as a third series of potential DXR inhibitors in very good yields (87% - 96%). Finally, in order to exploit an additional binding pocket in the PƒDXR active site, a series of N-benzylated phosphoramidic derivatives were obtained in seven steps from the starting material, diethyl phosphoramidate. The known inhibitors, fosmidomycin and its acetyl derivative FR900098, were also successfully synthesised as standards for STD-NMR binding and inhibition assays. In all, over 200 compounds (136 novel) have been prepared and appropriately characterised using 1-and 2-D NMR and IR spectroscopic analysis and, where necessary, HRMS or combustion analysis. Saturation Transfer Difference (STD) protein-NMR experiments, undertaken using selected compounds, have revealed binding of most of the ligands examined to EcDXR. Computersimulated docking studies have also been used to explore the preferred ligand-binding conformations and interactions between the ligands and essential DXR active-site residues, while DXR-enzyme inhibition assays of selected synthesised ligands have revealed certain patterns of inhibitory activity.
- Full Text:
- Date Issued: 2011
- Authors: Mutorwa, Marius Kudumo
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Malaria -- Chemotherapy Drug development Lead compounds Phosphonates Phosphonic acids Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4372 , http://hdl.handle.net/10962/d1005037
- Description: This research has focused on the development of novel substrate mimics as potential DXR inhibitors of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), an essential enzyme in the mevalonate-independent pathway for the biosynthesis of isoprenoids in Plasmodium falciparum. DXR mediates the isomerisation and reduction of 1-deoxy-D-xylulose-5-phosphate (DOXP) into 2C-methyl-D-erithrytol 4-phosphate (MEP) and has been validated as an attractive target for the development of novel anti-malarial chemotherapeutic agents. Reaction of various amines with specially prepared 4-phosphonated crotonic acid in the presence of the peptide coupling reagent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), has afforded a series of amido-phosphonate esters in moderate to good yields (48% - 73%) which, using a RuCl₃/CeCl₃/NaIO₄ catalyst system, have been dihydroxylated to furnish the dihydroxy-amido phosphonate ester pro-drugs; subsequent hydrolysis under microwave irradiation has afforded the corresponding phosphonic acids. A second series of potential inhibitors viz., 3-substituted aniline-derived phosphonate esters, their corresponding phosphonic acids and mono-sodium salts, have also been successfully synthesised. In these compounds, the essential functional groups are separated by one, two, three or four methylene groups, Deprotonation of the 3-substituted aniline substrates, followed by reaction with the appropriate ω-chloroalkanoyl chloride produced the ω-chloroamide intermediates, which were subjected to the Michaelis-Arbuzov reaction to afford the diethyl phosphonate esters in moderate to good yields (48% - 74%). Microwave-assisted TMSBrmediated cleavage of the phosphonate esters furnished the phosphonic acids, neutralisation of which afforded the mono-sodium salts. Furan-derived phosphate esters and phosphonic acids have been prepared as conformationally-restricted DOXP analogues. Functionalization at C-5 of the trityl-protected furan was achieved using the Vilsmeier-Haack formylation and Friedel-Crafts acylation reactions and, following de-tritylation, phosphorylation and oximation, using hydroxylamine hydrochloride, the novel oxime derivatives have been isolated as a third series of potential DXR inhibitors in very good yields (87% - 96%). Finally, in order to exploit an additional binding pocket in the PƒDXR active site, a series of N-benzylated phosphoramidic derivatives were obtained in seven steps from the starting material, diethyl phosphoramidate. The known inhibitors, fosmidomycin and its acetyl derivative FR900098, were also successfully synthesised as standards for STD-NMR binding and inhibition assays. In all, over 200 compounds (136 novel) have been prepared and appropriately characterised using 1-and 2-D NMR and IR spectroscopic analysis and, where necessary, HRMS or combustion analysis. Saturation Transfer Difference (STD) protein-NMR experiments, undertaken using selected compounds, have revealed binding of most of the ligands examined to EcDXR. Computersimulated docking studies have also been used to explore the preferred ligand-binding conformations and interactions between the ligands and essential DXR active-site residues, while DXR-enzyme inhibition assays of selected synthesised ligands have revealed certain patterns of inhibitory activity.
- Full Text:
- Date Issued: 2011
The development of novel cancer targeting agents
- Authors: Knoetze, Steyn
- Date: 2011
- Subjects: Cancer -- Research , Cancer -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10397 , http://hdl.handle.net/10948/d1010636 , Cancer -- Research , Cancer -- Treatment
- Description: The search for the cure for cancer is currently a multi-billion dollar industry and the search for the elusive “magic bullet”, i.e. the perfect cancer drug that would interact therapeutically with cancerous tissues while having a minimal effect on healthy cells, is the topic of many research studies in the world today. A large number of novel drugs or drug complexes and conjugates are being synthesized and subjected to rigorous evaluation in the race to find the perfect cure. ECDG (Ethylene diCysteine DeoxyGlucose) seems to have promising cancer targeting ability. Even though this compound has been described in a few publications, we could not find any reference to the current use of ECDG in oncology clinics, either as a therapeutic agent, or as a diagnostic tool for imaging purposes. It was also not possible to purchase pure ECDG anywhere in the world. This prompted us to further investigate ECDG as a possible candidate for cancer targeting research, either as an imaging agent for cancer diagnosis or complexed with an anti-cancer agent for therapeutic purposes. Detailed investigations done in our laboratory can be divided into the following categories: - Development of a synthetic method for ECDG on a multigram scale ; - Purification of prepared ECDG not using the described dialysis method that only allows the purification of small quantities of ECDG (mg scale) ; Detailed investigation of the chemistry involved in the preparation of pure ECDG and its metal complexes ; - Investigation of the stability of ECDG and its metal complexes that is essential data required for any pharmaceutical agent ; - Preparation of ECDG complexes for use as a diagnostic tool, i.e. complexation with 99mTc ; Investigation of the bio distribution of ECDG-ReO complexes ; - Preparation of an ECDG kit as a diagnostic tool for use in oncology clinics. The development of novel aromatic ligands having similar characteristics compared to ECDG, containing an N2S2 chromophore as donor atoms, to further investigate their targeting capabilities, have also been investigated. All intermediates and final compounds were characterized mainly by ESI MS, in some cases IR and NMR whenever available. Successful preparation and purification of ECDG ands its metal complexes was achieved and extensively characterized and evaluated. Efforts directed towards the development of ECDG at NECSA, South Africa, were also rewarded with significant success. Furthermore, significant development regarding the synthesis of two novel compounds with ECDG-like characteristics was also completed.
- Full Text:
- Date Issued: 2011
- Authors: Knoetze, Steyn
- Date: 2011
- Subjects: Cancer -- Research , Cancer -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10397 , http://hdl.handle.net/10948/d1010636 , Cancer -- Research , Cancer -- Treatment
- Description: The search for the cure for cancer is currently a multi-billion dollar industry and the search for the elusive “magic bullet”, i.e. the perfect cancer drug that would interact therapeutically with cancerous tissues while having a minimal effect on healthy cells, is the topic of many research studies in the world today. A large number of novel drugs or drug complexes and conjugates are being synthesized and subjected to rigorous evaluation in the race to find the perfect cure. ECDG (Ethylene diCysteine DeoxyGlucose) seems to have promising cancer targeting ability. Even though this compound has been described in a few publications, we could not find any reference to the current use of ECDG in oncology clinics, either as a therapeutic agent, or as a diagnostic tool for imaging purposes. It was also not possible to purchase pure ECDG anywhere in the world. This prompted us to further investigate ECDG as a possible candidate for cancer targeting research, either as an imaging agent for cancer diagnosis or complexed with an anti-cancer agent for therapeutic purposes. Detailed investigations done in our laboratory can be divided into the following categories: - Development of a synthetic method for ECDG on a multigram scale ; - Purification of prepared ECDG not using the described dialysis method that only allows the purification of small quantities of ECDG (mg scale) ; Detailed investigation of the chemistry involved in the preparation of pure ECDG and its metal complexes ; - Investigation of the stability of ECDG and its metal complexes that is essential data required for any pharmaceutical agent ; - Preparation of ECDG complexes for use as a diagnostic tool, i.e. complexation with 99mTc ; Investigation of the bio distribution of ECDG-ReO complexes ; - Preparation of an ECDG kit as a diagnostic tool for use in oncology clinics. The development of novel aromatic ligands having similar characteristics compared to ECDG, containing an N2S2 chromophore as donor atoms, to further investigate their targeting capabilities, have also been investigated. All intermediates and final compounds were characterized mainly by ESI MS, in some cases IR and NMR whenever available. Successful preparation and purification of ECDG ands its metal complexes was achieved and extensively characterized and evaluated. Efforts directed towards the development of ECDG at NECSA, South Africa, were also rewarded with significant success. Furthermore, significant development regarding the synthesis of two novel compounds with ECDG-like characteristics was also completed.
- Full Text:
- Date Issued: 2011
Time series models for paired comparisons
- Authors: Sjolander, Morne Rowan
- Date: 2011
- Subjects: Paired comparisons (Statistics)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10577 , http://hdl.handle.net/10948/d1012858
- Description: The method of paired comparisons is seen as a technique used to rank a set of objects with respect to an abstract or immeasurable property. To do this, the objects get to be compared two at a time. The results are input into a model, resulting in numbers known as weights being assigned to the objects. The weights are then used to rank the objects. The method of paired comparisons was first used for psychometric investigations. Various other applications of the method are also present, for example economic applications, and applications in sports statistics. This study involves taking paired comparison models and making them time-dependent. Not much research has been done in this area. Three new time series models for paired comparisons are created. Simulations are done to support the evidence obtained, and theoretical as well as practical examples are given to illustrate the results and to verify the efficiency of the new models. A literature study is given on the method of paired comparisons, as well as on the areas in which we apply our models. Our first two time series models for paired comparisons are the Linear-Trend Bradley- Terry Model and the Sinusoidal Bradley-Terry Model. We use the maximum likelihood approach to solve these models. We test our models using exact and randomly simulated data for various time periods and various numbers of objects. We adapt the Linear-Trend Bradley-Terry Model and received our third time series model for paired comparisons, the Log Linear-Trend Bradley-Terry Model. The daily maximum and minimum temperatures were received for Port Elizabeth, Uitenhage and Coega for 2005 until 2009. To evaluate the performance of the Linear-Trend Bradley-Terry Model and the Sinusoidal Bradley-Terry Model on estimating missing temperature data, we artificially remove observations of temperature from Coega’s temperature dataset for 2006 until 2008, and use various forms of these models to estimate the missing data points. The exchange rates for 2005 until 2008 between the following currencies: the Rand, Dollar, Euro, Pound and Yen, were obtained and various forms of our Log Linear-Trend Bradley-Terry Model are used to forecast the exchange rate for one day ahead for each month in 2006 until 2008. One of the features of this study is that we apply our time series models for paired comparisons to areas which comprise non-standard paired comparisons; and we want to encourage the use of the method of paired comparisons in a broader sense than what it is traditionally used for. The results of this study can be used in various other areas, like for example, in sports statistics, to rank the strength of sports players and predict their future scores; in Physics, to calculate weather risks of electricity generation, particularly risks related to nuclear power plants, and so forth, as well as in many other areas. It is hoped that this research will open the door to much more research in combining time series analysis with the method of paired comparisons.
- Full Text:
- Date Issued: 2011
- Authors: Sjolander, Morne Rowan
- Date: 2011
- Subjects: Paired comparisons (Statistics)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10577 , http://hdl.handle.net/10948/d1012858
- Description: The method of paired comparisons is seen as a technique used to rank a set of objects with respect to an abstract or immeasurable property. To do this, the objects get to be compared two at a time. The results are input into a model, resulting in numbers known as weights being assigned to the objects. The weights are then used to rank the objects. The method of paired comparisons was first used for psychometric investigations. Various other applications of the method are also present, for example economic applications, and applications in sports statistics. This study involves taking paired comparison models and making them time-dependent. Not much research has been done in this area. Three new time series models for paired comparisons are created. Simulations are done to support the evidence obtained, and theoretical as well as practical examples are given to illustrate the results and to verify the efficiency of the new models. A literature study is given on the method of paired comparisons, as well as on the areas in which we apply our models. Our first two time series models for paired comparisons are the Linear-Trend Bradley- Terry Model and the Sinusoidal Bradley-Terry Model. We use the maximum likelihood approach to solve these models. We test our models using exact and randomly simulated data for various time periods and various numbers of objects. We adapt the Linear-Trend Bradley-Terry Model and received our third time series model for paired comparisons, the Log Linear-Trend Bradley-Terry Model. The daily maximum and minimum temperatures were received for Port Elizabeth, Uitenhage and Coega for 2005 until 2009. To evaluate the performance of the Linear-Trend Bradley-Terry Model and the Sinusoidal Bradley-Terry Model on estimating missing temperature data, we artificially remove observations of temperature from Coega’s temperature dataset for 2006 until 2008, and use various forms of these models to estimate the missing data points. The exchange rates for 2005 until 2008 between the following currencies: the Rand, Dollar, Euro, Pound and Yen, were obtained and various forms of our Log Linear-Trend Bradley-Terry Model are used to forecast the exchange rate for one day ahead for each month in 2006 until 2008. One of the features of this study is that we apply our time series models for paired comparisons to areas which comprise non-standard paired comparisons; and we want to encourage the use of the method of paired comparisons in a broader sense than what it is traditionally used for. The results of this study can be used in various other areas, like for example, in sports statistics, to rank the strength of sports players and predict their future scores; in Physics, to calculate weather risks of electricity generation, particularly risks related to nuclear power plants, and so forth, as well as in many other areas. It is hoped that this research will open the door to much more research in combining time series analysis with the method of paired comparisons.
- Full Text:
- Date Issued: 2011
Trophodynamics of the benthic and hyperbenthic communities inhabiting the Sub-Antarctic Prince Edward Islands : stable isotope and fatty acid signatures
- Authors: Allan, Elizabeth Louise
- Date: 2011
- Subjects: Benthos -- Prince Edward Islands Benthos -- Feeding and feeds -- Prince Edward Islands Benthos -- Nutrition -- Prince Edward Islands Prince Edward Islands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5806 , http://hdl.handle.net/10962/d1006350
- Description: The aim of this study was to investigate spatial changes in the trophic and energy pathways of the benthic community in the shallow shelf waters of the sub-Antarctic Prince Edward Islands (PEI). A combination of stable isotope and fatty acid analyses were used to provide a time-integrated view of the assimilated feeding history of selected components of the PEI benthic community. This study forms part of the larger project entitled “Variability in the Southern Ocean ecosystems” and is a contribution to the South African National Antarctic Programme (SANAP). During austral autumn 2009, benthic specimens were collected from 10 stations (from depths of 70 to 295 m) in different regions around the PEI: inter-island shelf (upstream, between and downstream of the islands) and nearshore. Historical data were combined with new data collected during 2009 to assess the long-term trends in the feeding ecology of the benthos in the region of the islands. The stable isotope and fatty acid signatures of the benthic suspension- and deposit-feeding organisms generated during this study suggested that these two communities incorporated both phytoplankton and kelp in their diets. Stable isotope, and to a lesser extent fatty acid signatures, indicated that kelp contributed more to the diets of those organisms in close proximity to the kelp beds (nearshore stations) than those from the inter-island region. Overall, however, pelagic phytoplankton was the dominant food source in the diets of all organisms, even for those living near the kelp beds. Notable exceptions were the sponges and bryozoans, in which kelp and phytoplankton contributed similar proportions to their diets, most likely resulting from a size restricted feeding mode. There were, therefore, no distinct spatial differences in the importance of the various food sources. However, fatty acid compositional data indicated increased food quality between and within the lee of the islands compared to upstream. The organisms collected upstream of the PEI had substantially lower quantities of total fatty acids (TFAs) than organisms of the same species collected from nearshore, open shelf or downstream stations. The increased food quality between and within the lee of the islands was likely a result of the “island mass effect”, which reflects increased phytoplankton concentrations at the PEI. The fatty acid profiles of hyperbenthic shrimp Nauticaris marionis, a key species in the PEI ecosystem, revealed no distinct ontogenetic or spatial patterns. This result is in contrast to the stable isotope analyses, which detected both spatial and ontogenetic differences in the diet of the shrimp. Nearshore shrimp were more ₁₃C-enriched than those from the inter-island region, suggesting increased kelp entering the food web within these regions. In addition, the shrimps demonstrated enrichment in δ₁₃C and δ₁₅N signatures with an increase in size, resulting in a relatively distinct separation of size classes, thus reflecting niche separation through their diets. The fatty acid profiles revealed that the shrimp all contained large proportions of polyunsaturated fatty acids (PUFAs) and essential fatty acids (EFAs), indicating that the quality of food consumed was similar among size class and region despite the niche separation and variation in carbon sources utilised. In addition, diatom and dinoflagellate fatty acids (20:5ω3 and 22:6ω3, respectively) occurred in the highest proportions in N. marionis, highlighting the importance of phytoplankton (indirectly) in their diet. These results represent strong evidence that phytoplankton is an importance food source in the PEI ecosystem. The temporal investigation of isotope signatures in the benthos at the PEI indicated that N. marionis demonstrated an overall depletion in δ₁₃C signatures over the period of 1984 to 2009 (nearshore: -2.55 ‰, inter-island: -2.32 ‰). Overall, the benthic community showed similar depletions in δ13C signatures (from -1.96 to -4.70 ‰), suggesting that shifts have occurred in the carbon signatures at the base of the food web. The depletion in δ₁₃C signatures of the benthos at the PEI most likely reflects increased contributions of smaller slow growing phytoplankton cells (more depleted signatures than large fast growing cells) in the diets of these organisms over time. These diet shifts, in turn, suggest a decrease in productivity has occurred at the islands, likely due to a decreased frequency and intensity of the “island mass effect”. Decreased phytoplankton productivity at the PEI likely results from the southward shift in the average position of the sub-Antarctic Front (SAF), most likely in response to climate change, which in turn promotes flow-through conditions rather than retention at the PEI.
- Full Text:
- Date Issued: 2011
- Authors: Allan, Elizabeth Louise
- Date: 2011
- Subjects: Benthos -- Prince Edward Islands Benthos -- Feeding and feeds -- Prince Edward Islands Benthos -- Nutrition -- Prince Edward Islands Prince Edward Islands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5806 , http://hdl.handle.net/10962/d1006350
- Description: The aim of this study was to investigate spatial changes in the trophic and energy pathways of the benthic community in the shallow shelf waters of the sub-Antarctic Prince Edward Islands (PEI). A combination of stable isotope and fatty acid analyses were used to provide a time-integrated view of the assimilated feeding history of selected components of the PEI benthic community. This study forms part of the larger project entitled “Variability in the Southern Ocean ecosystems” and is a contribution to the South African National Antarctic Programme (SANAP). During austral autumn 2009, benthic specimens were collected from 10 stations (from depths of 70 to 295 m) in different regions around the PEI: inter-island shelf (upstream, between and downstream of the islands) and nearshore. Historical data were combined with new data collected during 2009 to assess the long-term trends in the feeding ecology of the benthos in the region of the islands. The stable isotope and fatty acid signatures of the benthic suspension- and deposit-feeding organisms generated during this study suggested that these two communities incorporated both phytoplankton and kelp in their diets. Stable isotope, and to a lesser extent fatty acid signatures, indicated that kelp contributed more to the diets of those organisms in close proximity to the kelp beds (nearshore stations) than those from the inter-island region. Overall, however, pelagic phytoplankton was the dominant food source in the diets of all organisms, even for those living near the kelp beds. Notable exceptions were the sponges and bryozoans, in which kelp and phytoplankton contributed similar proportions to their diets, most likely resulting from a size restricted feeding mode. There were, therefore, no distinct spatial differences in the importance of the various food sources. However, fatty acid compositional data indicated increased food quality between and within the lee of the islands compared to upstream. The organisms collected upstream of the PEI had substantially lower quantities of total fatty acids (TFAs) than organisms of the same species collected from nearshore, open shelf or downstream stations. The increased food quality between and within the lee of the islands was likely a result of the “island mass effect”, which reflects increased phytoplankton concentrations at the PEI. The fatty acid profiles of hyperbenthic shrimp Nauticaris marionis, a key species in the PEI ecosystem, revealed no distinct ontogenetic or spatial patterns. This result is in contrast to the stable isotope analyses, which detected both spatial and ontogenetic differences in the diet of the shrimp. Nearshore shrimp were more ₁₃C-enriched than those from the inter-island region, suggesting increased kelp entering the food web within these regions. In addition, the shrimps demonstrated enrichment in δ₁₃C and δ₁₅N signatures with an increase in size, resulting in a relatively distinct separation of size classes, thus reflecting niche separation through their diets. The fatty acid profiles revealed that the shrimp all contained large proportions of polyunsaturated fatty acids (PUFAs) and essential fatty acids (EFAs), indicating that the quality of food consumed was similar among size class and region despite the niche separation and variation in carbon sources utilised. In addition, diatom and dinoflagellate fatty acids (20:5ω3 and 22:6ω3, respectively) occurred in the highest proportions in N. marionis, highlighting the importance of phytoplankton (indirectly) in their diet. These results represent strong evidence that phytoplankton is an importance food source in the PEI ecosystem. The temporal investigation of isotope signatures in the benthos at the PEI indicated that N. marionis demonstrated an overall depletion in δ₁₃C signatures over the period of 1984 to 2009 (nearshore: -2.55 ‰, inter-island: -2.32 ‰). Overall, the benthic community showed similar depletions in δ13C signatures (from -1.96 to -4.70 ‰), suggesting that shifts have occurred in the carbon signatures at the base of the food web. The depletion in δ₁₃C signatures of the benthos at the PEI most likely reflects increased contributions of smaller slow growing phytoplankton cells (more depleted signatures than large fast growing cells) in the diets of these organisms over time. These diet shifts, in turn, suggest a decrease in productivity has occurred at the islands, likely due to a decreased frequency and intensity of the “island mass effect”. Decreased phytoplankton productivity at the PEI likely results from the southward shift in the average position of the sub-Antarctic Front (SAF), most likely in response to climate change, which in turn promotes flow-through conditions rather than retention at the PEI.
- Full Text:
- Date Issued: 2011
A short composition portfolio
- Buitendag, Kingsley Alexander
- Authors: Buitendag, Kingsley Alexander
- Date: 2011
- Subjects: Music -- South Africa Composition (Music)
- Language: English
- Type: text , Thesis , Masters , MMus
- Identifier: vital:2632 , http://hdl.handle.net/10962/d1002297
- Full Text:
- Date Issued: 2011
- Authors: Buitendag, Kingsley Alexander
- Date: 2011
- Subjects: Music -- South Africa Composition (Music)
- Language: English
- Type: text , Thesis , Masters , MMus
- Identifier: vital:2632 , http://hdl.handle.net/10962/d1002297
- Full Text:
- Date Issued: 2011
Emplacement of the 2.44 Ga ultramafic layered Kemi intrusion, Finland PGE, geochemical and Sm-Nd isotopic implications
- Authors: Linkermann, Sean Aaron
- Date: 2011
- Subjects: Chromite -- Finland -- Kemi , Mining geology -- Finland -- Kemi , Geochemistry -- Finland -- Kemi , Petrology -- Finland -- Kemi
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4940 , http://hdl.handle.net/10962/d1005552 , Chromite -- Finland -- Kemi , Mining geology -- Finland -- Kemi , Geochemistry -- Finland -- Kemi , Petrology -- Finland -- Kemi
- Description: Europe’s largest chrome deposit is hosted by the 2.44 Ga Kemi ultramafic layered intrusion. The lower half of the intrusion consists of peridotites, pyroxenites and chromitite layers while the upper half consists of websterites, gabbronorites and leucogabbros. The mafic minerals of the lower and upper parts of the intrusion are altered to serpentine, chlorite, talc, amphiboles and carbonates. However, the original mineralogy is still preserved in the middle part of the intrusion. Earlier work on the Kemi intrusion concentrated mainly on the economically important chromitite layers and suggested that these layers were formed through contamination of a single pulse of primitive magma by underlying Archaean basement crustal material. The broad variations of the major element concentrations reflect variations in the mode of the Kemi rocks. The petrology, which shows olivine- and orthopyroxene-dominated rocks in the lower portion of the intrusion to plagioclase- and clinopyroxene-dominated rocks in the upper portion, shows a gross consistency with a fractional crystallization process.The incompatible elements are relatively enriched in the lower portion of the intrusion which is not consistent with a broad fractional crystallization process. These variations suggest that the ultramafic portion of the KemiIntrusion is relatively enriched in trapped liquid compared to the mafic portion.ε2.44 Nd values ranges from +4 (consistent with depleted mantle source) to -10 (indicating a contribution from Archaean crust). The lower peridotites, pyroxenites and websterites have ε2.44 Nd values ranging between depleted mantle signatures and -2, whereas the gabbroic cumulates have ε2.44 Nd values which cover a range from around -5 to -10. Nd isotopic variation in the lower part of the profile is punctuated by distinct spikes to lower ε2.44 Nd corresponding to the chromitite horizons. Both the lower and upper portions of the Kemi Intrusion show enrichment of LREEC1 relative to HREEC1. The LREEC1 enriched values start to increase markedly from about the 1000 meter mark and continue to increase in value towards the roof of the intrusion.The main enrichment of PGE (ΣPPGE = 55 to 148 ppb) occurs approximately 90 to 160 m above the basal contact, beginning within andcontinuing above the main chromitite ore horizon. The mantle-normalized PGE abundances of the main chromitite horizon and the peridotites and pyroxenites below it show enrichment of IPGEPM (Os + Ir + Ru) relative to PPGEPM (Rh + Pd + Pt). In contrast, the overlying rocks are characterised by enrichment of PPGEPM relative to IPGEPM. These PGE-patterns suggest the influence of two distinct controlling processes above and below the main chromitite reef.The isotopic data are consistent with the initial introduction of multiple pulses of depleted mantle-derived magma crystallising olivine and pyroxene. Before the parent magma was fed into the Kemi magma chamber, it underwent crustal contamination and assimilation in a staging chamber within the lower crust. Some of these pulses were “critically crustally contaminated”, inducing chromite saturation and precipitation. The modelling also predicts minor in-situ contamination of the parent magma in the Kemi chamber with its wall and roof rocks. Above the main chromitite layer (about 160 m above the basal contact), the chromite content decreases and the PPGEPM/IPGEPM values increase which is consistent with scavenging of the IPGE into the lowermost layers and/or evolving magma compositions. Above 1000 m, the isotopic and REE data indicate a new magma pulse which has also been extensively contaminated in the staging magma chamber before emplacement into the Kemi magma chamber. The contamination in the staging magma chamber increased which is reflected in a progressively larger crustal component towards the top of the Kemi Intrusion
- Full Text:
- Date Issued: 2011
- Authors: Linkermann, Sean Aaron
- Date: 2011
- Subjects: Chromite -- Finland -- Kemi , Mining geology -- Finland -- Kemi , Geochemistry -- Finland -- Kemi , Petrology -- Finland -- Kemi
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4940 , http://hdl.handle.net/10962/d1005552 , Chromite -- Finland -- Kemi , Mining geology -- Finland -- Kemi , Geochemistry -- Finland -- Kemi , Petrology -- Finland -- Kemi
- Description: Europe’s largest chrome deposit is hosted by the 2.44 Ga Kemi ultramafic layered intrusion. The lower half of the intrusion consists of peridotites, pyroxenites and chromitite layers while the upper half consists of websterites, gabbronorites and leucogabbros. The mafic minerals of the lower and upper parts of the intrusion are altered to serpentine, chlorite, talc, amphiboles and carbonates. However, the original mineralogy is still preserved in the middle part of the intrusion. Earlier work on the Kemi intrusion concentrated mainly on the economically important chromitite layers and suggested that these layers were formed through contamination of a single pulse of primitive magma by underlying Archaean basement crustal material. The broad variations of the major element concentrations reflect variations in the mode of the Kemi rocks. The petrology, which shows olivine- and orthopyroxene-dominated rocks in the lower portion of the intrusion to plagioclase- and clinopyroxene-dominated rocks in the upper portion, shows a gross consistency with a fractional crystallization process.The incompatible elements are relatively enriched in the lower portion of the intrusion which is not consistent with a broad fractional crystallization process. These variations suggest that the ultramafic portion of the KemiIntrusion is relatively enriched in trapped liquid compared to the mafic portion.ε2.44 Nd values ranges from +4 (consistent with depleted mantle source) to -10 (indicating a contribution from Archaean crust). The lower peridotites, pyroxenites and websterites have ε2.44 Nd values ranging between depleted mantle signatures and -2, whereas the gabbroic cumulates have ε2.44 Nd values which cover a range from around -5 to -10. Nd isotopic variation in the lower part of the profile is punctuated by distinct spikes to lower ε2.44 Nd corresponding to the chromitite horizons. Both the lower and upper portions of the Kemi Intrusion show enrichment of LREEC1 relative to HREEC1. The LREEC1 enriched values start to increase markedly from about the 1000 meter mark and continue to increase in value towards the roof of the intrusion.The main enrichment of PGE (ΣPPGE = 55 to 148 ppb) occurs approximately 90 to 160 m above the basal contact, beginning within andcontinuing above the main chromitite ore horizon. The mantle-normalized PGE abundances of the main chromitite horizon and the peridotites and pyroxenites below it show enrichment of IPGEPM (Os + Ir + Ru) relative to PPGEPM (Rh + Pd + Pt). In contrast, the overlying rocks are characterised by enrichment of PPGEPM relative to IPGEPM. These PGE-patterns suggest the influence of two distinct controlling processes above and below the main chromitite reef.The isotopic data are consistent with the initial introduction of multiple pulses of depleted mantle-derived magma crystallising olivine and pyroxene. Before the parent magma was fed into the Kemi magma chamber, it underwent crustal contamination and assimilation in a staging chamber within the lower crust. Some of these pulses were “critically crustally contaminated”, inducing chromite saturation and precipitation. The modelling also predicts minor in-situ contamination of the parent magma in the Kemi chamber with its wall and roof rocks. Above the main chromitite layer (about 160 m above the basal contact), the chromite content decreases and the PPGEPM/IPGEPM values increase which is consistent with scavenging of the IPGE into the lowermost layers and/or evolving magma compositions. Above 1000 m, the isotopic and REE data indicate a new magma pulse which has also been extensively contaminated in the staging magma chamber before emplacement into the Kemi magma chamber. The contamination in the staging magma chamber increased which is reflected in a progressively larger crustal component towards the top of the Kemi Intrusion
- Full Text:
- Date Issued: 2011
Records : history and genealogy of AmaCirha clan according to the Great House of the clan, beginning from the amaXhosa nation
- Date: 2011
- Subjects: Qangqolo, African chief Cirha (African people) -- South Africa -- History Ngcwanguba -- Eastern Cape -- South Africa -- History
- Language: English
- Type: text
- Identifier: http://hdl.handle.net/10962/41218 , vital:25066 , This manuscript is held at the Cory Library for Humanities Research at Rhodes University. For further information contact cory@ru.ac.za. The digitisation of this image was made possible through a generous grant received from the Andrew W. Mellon Foundation 2014-2017. , PR 10 381
- Description: History and genealogy of AmaCirha clan according to the Great House of the clan, beginning from the amaXhosa nation. Sent to Prof Jeff Peires, Acting Head of Cory Library by M. L. Dyibhishe in 2011. , Dyibhishe, M L (donor)
- Full Text:
- Date Issued: 2011
- Date: 2011
- Subjects: Qangqolo, African chief Cirha (African people) -- South Africa -- History Ngcwanguba -- Eastern Cape -- South Africa -- History
- Language: English
- Type: text
- Identifier: http://hdl.handle.net/10962/41218 , vital:25066 , This manuscript is held at the Cory Library for Humanities Research at Rhodes University. For further information contact cory@ru.ac.za. The digitisation of this image was made possible through a generous grant received from the Andrew W. Mellon Foundation 2014-2017. , PR 10 381
- Description: History and genealogy of AmaCirha clan according to the Great House of the clan, beginning from the amaXhosa nation. Sent to Prof Jeff Peires, Acting Head of Cory Library by M. L. Dyibhishe in 2011. , Dyibhishe, M L (donor)
- Full Text:
- Date Issued: 2011
Studies in South African marine molluscan chemistry
- Authors: Bromley, Candice Leigh
- Date: 2011
- Subjects: Mollusks -- South Africa , Marine invertebrates -- South Africa , Marine metabolites -- South Africa , Chemical oceanography -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4356 , http://hdl.handle.net/10962/d1005021
- Description: This thesis investigates the variability occurring in the secondary metabolites produced by three South African marine molluscs. Chapter Two discusses the isolation and spectroscopic structure elucidation of the metabolites isolated from two Siphonaria species. The re-investigation of Siphonaria capensis yielded siphonarienfuranone (2.2) as the only common polypropionate isolated from both the 1998 and 2009 collections of S. capensis from the same areas suggesting possible seasonal or genetic variation in polypropionate production. The sterol cholest-7-en-3,5,7- triol (2.33) was also isolated form the 2009 collection of S. capensis and this is the first time this compound has been isolated from a Siphonaria species. The second species, Siphonaria oculus is closely related to S. capensis and the investigation into the former’s secondary metaboliteproduction revealed 2.2 as a major metabolite suggesting an inter-species overlap in polypropionate production. Three new polypropionate metabolites, 2.35, 2.36 and 2.37 were also isolated from S. oculus. An unsuccessful attempt was made to establish the absolute configuration of 2.37 using the modified Mosher’s method and the limited amount of 2.37 available prevented any further attempts at resolving the absolute configuration of this compound. The 1H NMR analysis of the defensive mucus collected directly from S. oculus revealed the presence of the acyclic polypropionate 2.37 as a minor metabolite. The absence of characteristic signals for the furanone containing compounds 2.2, 2.35 and 2.36, might suggest that these compounds cyclise from a hypothetical acyclic precursor (2.38) during standard work up of bulk acetone extracts of Siphonaria species. Chapter Three discusses the re-isolation and spectroscopic structure elucidation of the metabolites isolated from the nudibranch, Leminda millecra. Three known natural products, millecrone A (3.1), 8-hydroxycalamenene (3.6) and cubebenone (3.8) were re-isolated from our 2010 collection of L. millecra, as well as the new minor metabolite 8-acetoxycalamenene (3.16). The cytotoxic prenylated toluquinones and toluhydroquinones (3.9-3.15) initially isolated from the 1998 collection of L. millecra were not found in the 2010 collection supporting the hypothesis that these compounds may be of fungal origin. L. millecra clearly shows variability in the compounds sequestered by this species with millecrone A (3.1) being the only common metabolite in the three investigations of L. millecra to date. An unsuccessful attempt was made to establish the absolute configuration of 3.1, 3.6 and 3.8 through initial LAH reduction of the ketone moiety contained in 3.1 and 3.8 and esterification of the resultant diastereomeric alcohol mixtures and the phenol functionality in 3.6 with (1S)-camphanic chloride. Crystallisation of the (S)- camphanate esters of 3.6 and 3.8 for X-ray analysis were unsuccessful, while the unexpected conjugate addition of a hydride in 3.1 resulted in complex diastereomeric mixtures which could not be separated by HPLC.
- Full Text:
- Date Issued: 2011
- Authors: Bromley, Candice Leigh
- Date: 2011
- Subjects: Mollusks -- South Africa , Marine invertebrates -- South Africa , Marine metabolites -- South Africa , Chemical oceanography -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4356 , http://hdl.handle.net/10962/d1005021
- Description: This thesis investigates the variability occurring in the secondary metabolites produced by three South African marine molluscs. Chapter Two discusses the isolation and spectroscopic structure elucidation of the metabolites isolated from two Siphonaria species. The re-investigation of Siphonaria capensis yielded siphonarienfuranone (2.2) as the only common polypropionate isolated from both the 1998 and 2009 collections of S. capensis from the same areas suggesting possible seasonal or genetic variation in polypropionate production. The sterol cholest-7-en-3,5,7- triol (2.33) was also isolated form the 2009 collection of S. capensis and this is the first time this compound has been isolated from a Siphonaria species. The second species, Siphonaria oculus is closely related to S. capensis and the investigation into the former’s secondary metaboliteproduction revealed 2.2 as a major metabolite suggesting an inter-species overlap in polypropionate production. Three new polypropionate metabolites, 2.35, 2.36 and 2.37 were also isolated from S. oculus. An unsuccessful attempt was made to establish the absolute configuration of 2.37 using the modified Mosher’s method and the limited amount of 2.37 available prevented any further attempts at resolving the absolute configuration of this compound. The 1H NMR analysis of the defensive mucus collected directly from S. oculus revealed the presence of the acyclic polypropionate 2.37 as a minor metabolite. The absence of characteristic signals for the furanone containing compounds 2.2, 2.35 and 2.36, might suggest that these compounds cyclise from a hypothetical acyclic precursor (2.38) during standard work up of bulk acetone extracts of Siphonaria species. Chapter Three discusses the re-isolation and spectroscopic structure elucidation of the metabolites isolated from the nudibranch, Leminda millecra. Three known natural products, millecrone A (3.1), 8-hydroxycalamenene (3.6) and cubebenone (3.8) were re-isolated from our 2010 collection of L. millecra, as well as the new minor metabolite 8-acetoxycalamenene (3.16). The cytotoxic prenylated toluquinones and toluhydroquinones (3.9-3.15) initially isolated from the 1998 collection of L. millecra were not found in the 2010 collection supporting the hypothesis that these compounds may be of fungal origin. L. millecra clearly shows variability in the compounds sequestered by this species with millecrone A (3.1) being the only common metabolite in the three investigations of L. millecra to date. An unsuccessful attempt was made to establish the absolute configuration of 3.1, 3.6 and 3.8 through initial LAH reduction of the ketone moiety contained in 3.1 and 3.8 and esterification of the resultant diastereomeric alcohol mixtures and the phenol functionality in 3.6 with (1S)-camphanic chloride. Crystallisation of the (S)- camphanate esters of 3.6 and 3.8 for X-ray analysis were unsuccessful, while the unexpected conjugate addition of a hydride in 3.1 resulted in complex diastereomeric mixtures which could not be separated by HPLC.
- Full Text:
- Date Issued: 2011
Surface properties and electrocatalytic applications of metallophthalocyanines confined on electrode surfaces
- Authors: Akinbulu, Isaac Adebayo
- Date: 2011
- Subjects: Phthalocyanines Electrochemistry Electrocatalysis Pesticides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4365 , http://hdl.handle.net/10962/d1005030
- Description: New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.
- Full Text:
- Date Issued: 2011
- Authors: Akinbulu, Isaac Adebayo
- Date: 2011
- Subjects: Phthalocyanines Electrochemistry Electrocatalysis Pesticides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4365 , http://hdl.handle.net/10962/d1005030
- Description: New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.
- Full Text:
- Date Issued: 2011
An investigation into the state-of-practice of information security within Zambian copper mines: a case study
- Authors: Lukweza, Chishala
- Date: 2011
- Subjects: Computer security -- Zambia -- Management Case studies , Computer networks -- Security measures -- Zambia Case studies , Copper mines and mining -- Computer networks -- Security measures -- Zambia Case studies , Information technology -- Zambia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:1146 , http://hdl.handle.net/10962/d1002776 , Computer security -- Zambia -- Management Case studies , Computer networks -- Security measures -- Zambia Case studies , Copper mines and mining -- Computer networks -- Security measures -- Zambia Case studies , Information technology -- Zambia
- Description: Zambian copper mines have embraced the use of information technologies for strategic operations and competitive advantage. This dependence on these technologies has not only been seen in the physical aspects of business operations but also in the use of information systems such as Enterprise Resource Planning Systems (ERPs) for strategic decision making and increased usage of Industrial Control Systems (ICS’) that are meant to enhance operational efficiency in production areas. A survey was conducted to explore leadership perceptions on information security practices in Zambian copper mines and an ISO/IEC 27002 Audit Tool was administered to middle management in a particular mine for an in-depth analysis of their information security practices. Results revealed that although information security controls may have been put in place in these organisations, there are still areas that require attention. Senior management and middle management have different perceptions as to the extent to which information security practices are conducted in these copper mines. This implies that management may not be fully involved in certain aspects of these organisations’ information security practices. The results concluded that management needs to be fully involved and provide support for information security programs. Furthermore, these information security programs should be standardised so as to effectively protect these organisations’ information assets. This should also include the involvement of personnel as key players in the information security process.
- Full Text:
- Date Issued: 2011
- Authors: Lukweza, Chishala
- Date: 2011
- Subjects: Computer security -- Zambia -- Management Case studies , Computer networks -- Security measures -- Zambia Case studies , Copper mines and mining -- Computer networks -- Security measures -- Zambia Case studies , Information technology -- Zambia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:1146 , http://hdl.handle.net/10962/d1002776 , Computer security -- Zambia -- Management Case studies , Computer networks -- Security measures -- Zambia Case studies , Copper mines and mining -- Computer networks -- Security measures -- Zambia Case studies , Information technology -- Zambia
- Description: Zambian copper mines have embraced the use of information technologies for strategic operations and competitive advantage. This dependence on these technologies has not only been seen in the physical aspects of business operations but also in the use of information systems such as Enterprise Resource Planning Systems (ERPs) for strategic decision making and increased usage of Industrial Control Systems (ICS’) that are meant to enhance operational efficiency in production areas. A survey was conducted to explore leadership perceptions on information security practices in Zambian copper mines and an ISO/IEC 27002 Audit Tool was administered to middle management in a particular mine for an in-depth analysis of their information security practices. Results revealed that although information security controls may have been put in place in these organisations, there are still areas that require attention. Senior management and middle management have different perceptions as to the extent to which information security practices are conducted in these copper mines. This implies that management may not be fully involved in certain aspects of these organisations’ information security practices. The results concluded that management needs to be fully involved and provide support for information security programs. Furthermore, these information security programs should be standardised so as to effectively protect these organisations’ information assets. This should also include the involvement of personnel as key players in the information security process.
- Full Text:
- Date Issued: 2011
Preparation of photocatalytic TiO₂ nanoparticles immobilized on carbon nanofibres for water purification
- Authors: Nyamukamba, Pardon
- Date: 2011
- Subjects: Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11330 , http://hdl.handle.net/10353/367 , Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Description: Titanium dioxide nanoparticles were prepared using the sol-gel process. The effect of temperature and precursor concentration on particle size was investigated. The optimum conditions were then used to prepare carbon and nitrogen doped titanium dioxide (TiO2) nanoparticles. Doping was done to reduce band gap of the nanoparticles in order to utilize visible light in the photocatalytic degradation of organic compounds. A significant shift of the absorption edge to a longer wavelength (lower energy) from 420 nm to 456 nm and 420 nm to 428 nm was observed for the carbon doped and nitrogen doped TiO2 respectively. In this study, the prepared TiO2 photocatalyst was immobilized on carbon nanofibres to allow isolation and reuse of catalyst. The photocatalytic activity of the catalyst was tested using methyl orange as a model pollutant and was based on the decolourization of the dye as it was degraded. The doped TiO2 exhibited higher photocatalytic activity than the undoped TiO2. The materials prepared were characterized by XRD, TEM, SEM, FT-IR, DSC and TGA while the doped TiO2 was characterized by XPS, ESR and Raman Spectroscopy.
- Full Text:
- Date Issued: 2011
- Authors: Nyamukamba, Pardon
- Date: 2011
- Subjects: Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11330 , http://hdl.handle.net/10353/367 , Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Description: Titanium dioxide nanoparticles were prepared using the sol-gel process. The effect of temperature and precursor concentration on particle size was investigated. The optimum conditions were then used to prepare carbon and nitrogen doped titanium dioxide (TiO2) nanoparticles. Doping was done to reduce band gap of the nanoparticles in order to utilize visible light in the photocatalytic degradation of organic compounds. A significant shift of the absorption edge to a longer wavelength (lower energy) from 420 nm to 456 nm and 420 nm to 428 nm was observed for the carbon doped and nitrogen doped TiO2 respectively. In this study, the prepared TiO2 photocatalyst was immobilized on carbon nanofibres to allow isolation and reuse of catalyst. The photocatalytic activity of the catalyst was tested using methyl orange as a model pollutant and was based on the decolourization of the dye as it was degraded. The doped TiO2 exhibited higher photocatalytic activity than the undoped TiO2. The materials prepared were characterized by XRD, TEM, SEM, FT-IR, DSC and TGA while the doped TiO2 was characterized by XPS, ESR and Raman Spectroscopy.
- Full Text:
- Date Issued: 2011
Synthesis and photophysical studies of phthalocyanine–gold nanoparticle conjugates
- Nombona, Nolwazi, Antunes, Edith M, Litwinski, Christian, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
- Full Text:
- Date Issued: 2011
- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
- Full Text:
- Date Issued: 2011