Ruthenium (II) complexes of mixed bipyridyl and dithiolate/thiourea ligands :|bsynthesis, characterization, photophysical and electrochemical studies
- Authors: Nkombi, Pelokazi
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/10134 , vital:35358
- Description: Energy is one of the most important factor to influence human lives. The increased in energy demand as well as the detrimental effects posed by emission of greenhouse gases due to continue use of fossil fuels for electricity generation has led to a renewed focus on energy production using renewable energy sources which are relatively cheap, clean and environmentally sustainable. Among the various renewable energy sources used so far, the Dye Synthesized Solar Cells (DSSCs), a form of photovoltaic device is reported for their better efficiencies despite their low cost of production and ability to work relatively under low light conditions. A recent report on the solar-to-electricity conversion efficiency of a typical DSSC sensitizer made from zinc based porphyrin dye coupled with sintered titanium(IV) oxide as semiconductor was 13 percent. In this study, 2,2-bipyridyl-4,4-dicarboxylic acid (bpydc) was used as mixed ligand and four dithiolate ligands; L1 = dipotassium ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate, L2 = dipotassium bis(ethoxycarbonyl)ethane-2,2-dithiolate, L3 = dipotassium cyanodithio imidocarbonate and L4 = dipotassium 2,2-dicyanoethylene-2,2-dithiolate were synthesized while four alkyl thiourea ligands, L5 = 1,3-dimethyl thiourea, L6 = 1,3-diethyl thiourea, L7 = 1,3-diisopropyl thiourea and L8 = 1-methyl thiourea were purchased and used as supplied without further purification. These ligands were used to prepare eight ruthenium(II) complexes of mixed bipyridyl/dithiolate/thiourea. The compounds were characterised by elemental analysis and spectroscopic techniques, namely: Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR), ultraviolet-visible and photoluminescence (PL). Cyclic voltammetry (CV) and square wave voltammetry (SWV) were used for the electrochemical studies. Photoluminescence and UV-Vis spectroscopies were used for geometric and photophysical studies of the complexes respectively. FTIR spectra confirmed presence of functional groups in ligands and coordination of these ligands to ruthenium(II) ions to form complexes. The UV-Vis confirmed that the Ru(II) dithiolene complexes exhibited square planar geometries while the Ru(II) thiourea complexes gave octahedral geometries, this was deduced from the transitions assigned to the complexes. All the ruthenium(II) complexes synthesized showed photoluminescence properties that are suitable for light harvesting and application for dye-sensitized solar cells. Cyclic and square wave voltammetry show Ru(II) thiourea complexes have better redox properties when compared to Ru(II) dithiolate complexes which is ascribed to ligand strength field possibly due to contribution from the two bonded NCS groups.
- Full Text:
- Date Issued: 2018
- Authors: Nkombi, Pelokazi
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/10134 , vital:35358
- Description: Energy is one of the most important factor to influence human lives. The increased in energy demand as well as the detrimental effects posed by emission of greenhouse gases due to continue use of fossil fuels for electricity generation has led to a renewed focus on energy production using renewable energy sources which are relatively cheap, clean and environmentally sustainable. Among the various renewable energy sources used so far, the Dye Synthesized Solar Cells (DSSCs), a form of photovoltaic device is reported for their better efficiencies despite their low cost of production and ability to work relatively under low light conditions. A recent report on the solar-to-electricity conversion efficiency of a typical DSSC sensitizer made from zinc based porphyrin dye coupled with sintered titanium(IV) oxide as semiconductor was 13 percent. In this study, 2,2-bipyridyl-4,4-dicarboxylic acid (bpydc) was used as mixed ligand and four dithiolate ligands; L1 = dipotassium ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate, L2 = dipotassium bis(ethoxycarbonyl)ethane-2,2-dithiolate, L3 = dipotassium cyanodithio imidocarbonate and L4 = dipotassium 2,2-dicyanoethylene-2,2-dithiolate were synthesized while four alkyl thiourea ligands, L5 = 1,3-dimethyl thiourea, L6 = 1,3-diethyl thiourea, L7 = 1,3-diisopropyl thiourea and L8 = 1-methyl thiourea were purchased and used as supplied without further purification. These ligands were used to prepare eight ruthenium(II) complexes of mixed bipyridyl/dithiolate/thiourea. The compounds were characterised by elemental analysis and spectroscopic techniques, namely: Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR), ultraviolet-visible and photoluminescence (PL). Cyclic voltammetry (CV) and square wave voltammetry (SWV) were used for the electrochemical studies. Photoluminescence and UV-Vis spectroscopies were used for geometric and photophysical studies of the complexes respectively. FTIR spectra confirmed presence of functional groups in ligands and coordination of these ligands to ruthenium(II) ions to form complexes. The UV-Vis confirmed that the Ru(II) dithiolene complexes exhibited square planar geometries while the Ru(II) thiourea complexes gave octahedral geometries, this was deduced from the transitions assigned to the complexes. All the ruthenium(II) complexes synthesized showed photoluminescence properties that are suitable for light harvesting and application for dye-sensitized solar cells. Cyclic and square wave voltammetry show Ru(II) thiourea complexes have better redox properties when compared to Ru(II) dithiolate complexes which is ascribed to ligand strength field possibly due to contribution from the two bonded NCS groups.
- Full Text:
- Date Issued: 2018
An assessment of the invasion state and fisheries suitability in four dams and a natural lake in the Western Cape, South Africa
- Authors: Dredge, Brendon Neville
- Date: 2016
- Subjects: Introduced organisms Fishery management -- South Africa -- Western Cape Fishes -- Conservation -- South Africa -- Western Cape Introduced fishes -- South Africa -- Western Cape
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/69114 , vital:29391
- Description: Despite more than a century of introductions, fish invasions are poorly understood in South Africa. This thesis aims to: (1) provide baseline information on the fish fauna in five inland water bodies (four dams: Theewaterskloof, Clanwilliam, Quaggaskloof, and Voelvlei and a natural lake, Groenvlei) in the Western Cape; (2) determine which species were established and provide a baseline of abundance and size structure for monitoring and, (3) make preliminary recommendations for a fishery. First, criteria for determining establishment were developed by undertaking a full biological assessment of bluegill Lepomis macrochirus, a data-poor species in South Africa. This included the assessment of growth rate using validated estimates of age derived from otoliths in two dams (Clanwilliam Dam: Lt=335.9(1−eo.113(t+1.06)); Groenvlei: Lt=287.2(1-e−0.171(t+0.54)). Length at 50% maturity was similar for males (146 mmFL) and females (147 mmFL). Length frequency analysis combined with data on the age and growth and reproduction demonstrated that established populations of bluegill contained several age cohorts as well as mature and juvenile fishes. A meta-analysis was conducted to: (1) compile a list of initial stocking dates for all alien fishes in each waterbody and (2) use angler tournament data to assess for additional species and persistence over time. Data from the meta-analysis was combined with ichthyological survey data to determine establishment success. These data demonstrated that nine non-native species had established in the five water bodies. Clanwilliam Dam had the largest number (7) of non-native species established, Groenvlei (5) and Theewaterskloof, Brandvlei and Voelvlei the lowest with four species. The state of invasion of each species in the province showed that all nine species are categorised as invasive. This information on establishment was then integrated into a framework for rapidly determining what type of fishery would be most suitable for the 5 waterbodies. Potential yield was estimated using morphoedaphic models, were 260 t/yr for Theewaterskloof Dam, 93 t/yr for Voelvlei, 81 t/yr for Brandvlei, 59 t/yr for Groenvlei and 55 t/yr for Groenvlei. The CPUE for Groenvlei was the highest in gill nets with 1.32 ± 1.94 kg/h, then Voelvlei 1.05 ± 1.34 kg/h followed by Brandvlei (0.84 ± 1.48 kg/h), Clanwilliam (0.71 ± 1.55 kg/h) and lastly Theewaterskloof (0.36 ± 0.41 kg/h). Only Theewaterskloof could produce in excess of 100 t/yr but less than 400 t/yr of fish making it suitable for a small scale fishery. The CPUE values of Theewaterskloof were the lowest and a gill net fishery on this water body may not produce sufficient fish for the fishery. All water bodies had a high recreational angling usage, the opening of a small scale fishery could be detrimental to this industry. Subsistence and recreational anglers should be promoted with the possibility of a long line industry targeting Clarias gariepinus.
- Full Text:
- Date Issued: 2016
- Authors: Dredge, Brendon Neville
- Date: 2016
- Subjects: Introduced organisms Fishery management -- South Africa -- Western Cape Fishes -- Conservation -- South Africa -- Western Cape Introduced fishes -- South Africa -- Western Cape
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/69114 , vital:29391
- Description: Despite more than a century of introductions, fish invasions are poorly understood in South Africa. This thesis aims to: (1) provide baseline information on the fish fauna in five inland water bodies (four dams: Theewaterskloof, Clanwilliam, Quaggaskloof, and Voelvlei and a natural lake, Groenvlei) in the Western Cape; (2) determine which species were established and provide a baseline of abundance and size structure for monitoring and, (3) make preliminary recommendations for a fishery. First, criteria for determining establishment were developed by undertaking a full biological assessment of bluegill Lepomis macrochirus, a data-poor species in South Africa. This included the assessment of growth rate using validated estimates of age derived from otoliths in two dams (Clanwilliam Dam: Lt=335.9(1−eo.113(t+1.06)); Groenvlei: Lt=287.2(1-e−0.171(t+0.54)). Length at 50% maturity was similar for males (146 mmFL) and females (147 mmFL). Length frequency analysis combined with data on the age and growth and reproduction demonstrated that established populations of bluegill contained several age cohorts as well as mature and juvenile fishes. A meta-analysis was conducted to: (1) compile a list of initial stocking dates for all alien fishes in each waterbody and (2) use angler tournament data to assess for additional species and persistence over time. Data from the meta-analysis was combined with ichthyological survey data to determine establishment success. These data demonstrated that nine non-native species had established in the five water bodies. Clanwilliam Dam had the largest number (7) of non-native species established, Groenvlei (5) and Theewaterskloof, Brandvlei and Voelvlei the lowest with four species. The state of invasion of each species in the province showed that all nine species are categorised as invasive. This information on establishment was then integrated into a framework for rapidly determining what type of fishery would be most suitable for the 5 waterbodies. Potential yield was estimated using morphoedaphic models, were 260 t/yr for Theewaterskloof Dam, 93 t/yr for Voelvlei, 81 t/yr for Brandvlei, 59 t/yr for Groenvlei and 55 t/yr for Groenvlei. The CPUE for Groenvlei was the highest in gill nets with 1.32 ± 1.94 kg/h, then Voelvlei 1.05 ± 1.34 kg/h followed by Brandvlei (0.84 ± 1.48 kg/h), Clanwilliam (0.71 ± 1.55 kg/h) and lastly Theewaterskloof (0.36 ± 0.41 kg/h). Only Theewaterskloof could produce in excess of 100 t/yr but less than 400 t/yr of fish making it suitable for a small scale fishery. The CPUE values of Theewaterskloof were the lowest and a gill net fishery on this water body may not produce sufficient fish for the fishery. All water bodies had a high recreational angling usage, the opening of a small scale fishery could be detrimental to this industry. Subsistence and recreational anglers should be promoted with the possibility of a long line industry targeting Clarias gariepinus.
- Full Text:
- Date Issued: 2016
Evaluating late payment-induced waste in South Africa through lean construction principles
- Authors: Akuffo-Ntow, Eric Ayesu
- Date: 2016
- Subjects: Construction industry -- South Africa -- Finance , Lean manufacturing -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8867 , vital:26437
- Description: Central to the sustainable and competitive growth of the South African construction industry is a predictable cash flow through on time payment by clients to contractors. However, chronic late payments, a recurring problem in the industry, especially in the public sector, is bringing untold hardship to contractors by derailing their competitiveness and also eroding the trust among the supply chain partners to the extent that some firms end up closing business in the industry. The situation is viewed from the lean construction perspective as an obstacle that is preventing the accrual of the required value to project parties in the construction industry. This research addresses the causes of late payments to contractors and the role of the quantity surveyor (QS) in terms of influencing early payment from a lean construction perspective. A mixed method approach was used for compiling the primary data for the study. Sequentially, one hundred and two (102) quantitative and twelve (12) interview questionnaires were administered to selected contractors and construction professionals working predominantly on public sector projects. The findings revealed that the approval process for evaluation and certification by the client- appointed agent and intermediary institutions is taking longer than contractually allowed, with parties independently undertaking their evaluation prior to the certification date. This is found to be adverse to achieving consensus on the values of the works for authorisation. Other significant barriers are the lack of funds to authorise payment, random auditor general’s documentation changes, lack of administrators’ system integration and capacity to handle cyclical payment processing. Also, contractors have been found to be in default of timeously submitting complete claim documents. It is therefore recommended that the client agents should partner with the contractor in regular design and documentation reviews, arranging the payment process and should also meet jointly to prepare monthly evaluations. In addition, contractors should be mentored from the onset of the project regarding all the necessary documentation and supporting documents that will be required by the client to ensure that payment approvals are not delayed. The payment authori-sation agent’s capacity should be enhanced through training and improved powers as a singular point of control to perform efficiently and their systems and processes should be integrated to ensure that all parties are implementing the same protocols.
- Full Text:
- Date Issued: 2016
- Authors: Akuffo-Ntow, Eric Ayesu
- Date: 2016
- Subjects: Construction industry -- South Africa -- Finance , Lean manufacturing -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8867 , vital:26437
- Description: Central to the sustainable and competitive growth of the South African construction industry is a predictable cash flow through on time payment by clients to contractors. However, chronic late payments, a recurring problem in the industry, especially in the public sector, is bringing untold hardship to contractors by derailing their competitiveness and also eroding the trust among the supply chain partners to the extent that some firms end up closing business in the industry. The situation is viewed from the lean construction perspective as an obstacle that is preventing the accrual of the required value to project parties in the construction industry. This research addresses the causes of late payments to contractors and the role of the quantity surveyor (QS) in terms of influencing early payment from a lean construction perspective. A mixed method approach was used for compiling the primary data for the study. Sequentially, one hundred and two (102) quantitative and twelve (12) interview questionnaires were administered to selected contractors and construction professionals working predominantly on public sector projects. The findings revealed that the approval process for evaluation and certification by the client- appointed agent and intermediary institutions is taking longer than contractually allowed, with parties independently undertaking their evaluation prior to the certification date. This is found to be adverse to achieving consensus on the values of the works for authorisation. Other significant barriers are the lack of funds to authorise payment, random auditor general’s documentation changes, lack of administrators’ system integration and capacity to handle cyclical payment processing. Also, contractors have been found to be in default of timeously submitting complete claim documents. It is therefore recommended that the client agents should partner with the contractor in regular design and documentation reviews, arranging the payment process and should also meet jointly to prepare monthly evaluations. In addition, contractors should be mentored from the onset of the project regarding all the necessary documentation and supporting documents that will be required by the client to ensure that payment approvals are not delayed. The payment authori-sation agent’s capacity should be enhanced through training and improved powers as a singular point of control to perform efficiently and their systems and processes should be integrated to ensure that all parties are implementing the same protocols.
- Full Text:
- Date Issued: 2016
In vitro evaluation of antimicrobial and antioxidant activities of olea europaea subsp. africana and euryops brevipapposus used by Cala community folkloric medicine for the management of infections associated with chronic non-communicable diseases
- Authors: Adegborioye, Abiodun
- Date: 2016
- Subjects: Antioxidants , Medicinal plants , Traditional medicine -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/4869 , vital:28624
- Description: Chronic non-communicable diseses are a global public health challenge that continuously threatens the development and health of humans. Risk factors such as unbalanced diet-the high consumption of processed food or food from animal origin are responsible for NCDs. NCDs result in weakened immune system, making the host susceptible to opportunistic infections. Thus, the NCDs burden is most times chronic and multiple with the illness and suffering of the affected person numerous. The lack of cure for NCDs, the high cost of drugs, their high side-effects, and the emergence of multiple drug resistance has given rise to the investigation of other sources for therapeutic cure such as medicinal plants. The ethanol, n-hexane and ethyl acetate extracts of Olea europaea were analysed for their antioxidant and antimicrobial activities. The essential oil was also analysed for their chemical constituents. The n-hexane extracts of O. europaea exhibited no inhibition against all of the microorganisms tested, while the ethyl acetate and ethanol extracts exhibited inhibition, with minimum inhibitory concentration values between 0.625 mg/ml to 1.25 mg/ml. The ethanol leaf and ethyl acetate stem extracts exhibited significant activity in the inhibition of 2, 2-azinobis-(3-ethylbenzothiazolin - 6-sulfonic acid diammonium salt (ABTS) free radical, the n-hexane leaf extract had the overall significant lipid peroxidation inhibition activity, while in the inhibition of 2, 2- diphenyl-1-picrylhydrazyl radical (DPPH), the ethanol and ethyl acetate leaf extracts had strong activity. Nonanal, phytol, α-Pinene, α-Phellandrene, spatulenol and farnesol were some of chemical components identified after the GC-MS analysis of O. europaea oil. In the final part of the dissertation, Euryops brevipapposus essential oil was assessed for the antioxidant activities using free radical scavenging assays. In addition to this, the antimicrobial activities were assessed and the chemical composition was analysed using GC-MS. The essential oil demonstrated significant antioxidant activity against 2, 2-diphenyl-2-picryl-hydrazyl free radical (DPPH), 2, 2′-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) and lipid peroxides with IC50 value of 0.0000000671 mg/ml, 1.05 mg/ml, and 1.170 mg/ml respectively. The essential oil also showed significant activity against all microorganisms tested with minimum inhibitory concentration (MIC) values between 0.055 mg/ml to 0.5 mg/ml. α-pinene, α- Phellandrene, germacrene D, β-pinene, trans- β.-Ocimene, bicyclogermacrene and β -Phellandrene were some of the chemical compounds identified in E. brevipapposus oil. The study has shown that E. brevipapposus and O. europaea are abundant in phytochemical compounds which were thought to be the root cause for the activities demonstrated. Therefore, these therapeutic properties observed validate and elucidate the traditional usage of the both plants in the treatment /management of diseases.
- Full Text:
- Date Issued: 2016
- Authors: Adegborioye, Abiodun
- Date: 2016
- Subjects: Antioxidants , Medicinal plants , Traditional medicine -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/4869 , vital:28624
- Description: Chronic non-communicable diseses are a global public health challenge that continuously threatens the development and health of humans. Risk factors such as unbalanced diet-the high consumption of processed food or food from animal origin are responsible for NCDs. NCDs result in weakened immune system, making the host susceptible to opportunistic infections. Thus, the NCDs burden is most times chronic and multiple with the illness and suffering of the affected person numerous. The lack of cure for NCDs, the high cost of drugs, their high side-effects, and the emergence of multiple drug resistance has given rise to the investigation of other sources for therapeutic cure such as medicinal plants. The ethanol, n-hexane and ethyl acetate extracts of Olea europaea were analysed for their antioxidant and antimicrobial activities. The essential oil was also analysed for their chemical constituents. The n-hexane extracts of O. europaea exhibited no inhibition against all of the microorganisms tested, while the ethyl acetate and ethanol extracts exhibited inhibition, with minimum inhibitory concentration values between 0.625 mg/ml to 1.25 mg/ml. The ethanol leaf and ethyl acetate stem extracts exhibited significant activity in the inhibition of 2, 2-azinobis-(3-ethylbenzothiazolin - 6-sulfonic acid diammonium salt (ABTS) free radical, the n-hexane leaf extract had the overall significant lipid peroxidation inhibition activity, while in the inhibition of 2, 2- diphenyl-1-picrylhydrazyl radical (DPPH), the ethanol and ethyl acetate leaf extracts had strong activity. Nonanal, phytol, α-Pinene, α-Phellandrene, spatulenol and farnesol were some of chemical components identified after the GC-MS analysis of O. europaea oil. In the final part of the dissertation, Euryops brevipapposus essential oil was assessed for the antioxidant activities using free radical scavenging assays. In addition to this, the antimicrobial activities were assessed and the chemical composition was analysed using GC-MS. The essential oil demonstrated significant antioxidant activity against 2, 2-diphenyl-2-picryl-hydrazyl free radical (DPPH), 2, 2′-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) and lipid peroxides with IC50 value of 0.0000000671 mg/ml, 1.05 mg/ml, and 1.170 mg/ml respectively. The essential oil also showed significant activity against all microorganisms tested with minimum inhibitory concentration (MIC) values between 0.055 mg/ml to 0.5 mg/ml. α-pinene, α- Phellandrene, germacrene D, β-pinene, trans- β.-Ocimene, bicyclogermacrene and β -Phellandrene were some of the chemical compounds identified in E. brevipapposus oil. The study has shown that E. brevipapposus and O. europaea are abundant in phytochemical compounds which were thought to be the root cause for the activities demonstrated. Therefore, these therapeutic properties observed validate and elucidate the traditional usage of the both plants in the treatment /management of diseases.
- Full Text:
- Date Issued: 2016
A flight of fancy in the Chorister Robin-Chat (Cossypha dichroa) : an isotopic standpoint
- Wolmarans, Milena Helena Louise
- Authors: Wolmarans, Milena Helena Louise
- Date: 2015
- Subjects: Muscicapidae -- South Africa , Muscicapidae -- Food , Muscicapidae -- Habitat , Muscicapidae -- Habitat -- Conservation , Forest birds -- South Africa , Isotopes , Stable isotope tracers
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5920 , http://hdl.handle.net/10962/d1017207
- Description: Forested areas have been cited for their highly diverse floral and faunal assemblages, which are currently under threat from anthropogenic activities that restrict their range and deplete the resources produced within these naturally fragmented patches. Historically, up to 67 percent of avifaunal species associated with well-treed areas have undergone localised extinctions, consequentially affecting biodiversity as a measure of species richness and ecosystem functionality. To date, more than 900 of the bird species affiliated with forests are under threat and despite the theory surrounding functional redundancy, the mass extinction that is currently underway poses considerable limitations on the ecological integrity of these biomes. In South Africa, indigenous forest (one of the rarest biomes), occurs predominantly in small isolated patches along the eastern escarpment. With mountainous terrain emphasised as ‘prominent hotspots of extinction’, the limited dispersal and habitat sensitivity of montane forest fauna renders these species more prone to localised extinctions. BirdLife International, the IUCN and SABAP2 all indicate reductions in the range and abundance of the Chorister Robin-Chat (Cossypha dichroa) - an endemic forest specialist that is reported to move seasonally between high-altitude forest patches where they breed in summer, and lowland coastal forests where they overwinter. Beyond diet, body morphology and vocalisations, much of the information available on the altitudinal movements of C. dichroa is based on secondary sources and the assumptions therein. This study aimed to investigate the potential utilisation of δ13C and δ15N stable isotopes in determining the dietary niche width and altitudinal movements of C. dichroa. Feathers obtained in forested patches of the Limpopo, KwaZulu-Natal and Eastern Cape provinces exhibited a wide trophic niche width and generalised diet. Strong regional separation is apparent in the isotopic signatures suggesting little movement between provinces. A comparison of 13C-isotopes showed minimal variation that point to a uniformity in the carbon-base utilised by C. dichroa across their range. The 15N-signatures obtained in Limpopo, however, revealed a distinct trophic segregation between the northern-most Chorister populations and their southern counterparts. No altitudinal movements were detected in the isotopic signatures of recaptured Choristers, but more research is needed to investigate the long-term accuracy of these results and the breeding potential of resident Choristers in lowland coastal forests; especially when considering the reduced range and abundance reported for this endemic species.
- Full Text:
- Date Issued: 2015
- Authors: Wolmarans, Milena Helena Louise
- Date: 2015
- Subjects: Muscicapidae -- South Africa , Muscicapidae -- Food , Muscicapidae -- Habitat , Muscicapidae -- Habitat -- Conservation , Forest birds -- South Africa , Isotopes , Stable isotope tracers
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5920 , http://hdl.handle.net/10962/d1017207
- Description: Forested areas have been cited for their highly diverse floral and faunal assemblages, which are currently under threat from anthropogenic activities that restrict their range and deplete the resources produced within these naturally fragmented patches. Historically, up to 67 percent of avifaunal species associated with well-treed areas have undergone localised extinctions, consequentially affecting biodiversity as a measure of species richness and ecosystem functionality. To date, more than 900 of the bird species affiliated with forests are under threat and despite the theory surrounding functional redundancy, the mass extinction that is currently underway poses considerable limitations on the ecological integrity of these biomes. In South Africa, indigenous forest (one of the rarest biomes), occurs predominantly in small isolated patches along the eastern escarpment. With mountainous terrain emphasised as ‘prominent hotspots of extinction’, the limited dispersal and habitat sensitivity of montane forest fauna renders these species more prone to localised extinctions. BirdLife International, the IUCN and SABAP2 all indicate reductions in the range and abundance of the Chorister Robin-Chat (Cossypha dichroa) - an endemic forest specialist that is reported to move seasonally between high-altitude forest patches where they breed in summer, and lowland coastal forests where they overwinter. Beyond diet, body morphology and vocalisations, much of the information available on the altitudinal movements of C. dichroa is based on secondary sources and the assumptions therein. This study aimed to investigate the potential utilisation of δ13C and δ15N stable isotopes in determining the dietary niche width and altitudinal movements of C. dichroa. Feathers obtained in forested patches of the Limpopo, KwaZulu-Natal and Eastern Cape provinces exhibited a wide trophic niche width and generalised diet. Strong regional separation is apparent in the isotopic signatures suggesting little movement between provinces. A comparison of 13C-isotopes showed minimal variation that point to a uniformity in the carbon-base utilised by C. dichroa across their range. The 15N-signatures obtained in Limpopo, however, revealed a distinct trophic segregation between the northern-most Chorister populations and their southern counterparts. No altitudinal movements were detected in the isotopic signatures of recaptured Choristers, but more research is needed to investigate the long-term accuracy of these results and the breeding potential of resident Choristers in lowland coastal forests; especially when considering the reduced range and abundance reported for this endemic species.
- Full Text:
- Date Issued: 2015
Amber : a aero-interaction honeypot with distributed intelligence
- Authors: Schoeman, Adam
- Date: 2015
- Subjects: Security systems -- Security measures , Computer viruses , Intrusion detection systems (Computer security) , Computer security
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4716 , http://hdl.handle.net/10962/d1017938
- Description: For the greater part, security controls are based on the principle of Decision through Detection (DtD). The exception to this is a honeypot, which analyses interactions between a third party and itself, while occupying a piece of unused information space. As honeypots are not located on productive information resources, any interaction with it can be assumed to be non-productive. This allows the honeypot to make decisions based simply on the presence of data, rather than on the behaviour of the data. But due to limited resources in human capital, honeypots’ uptake in the South African market has been underwhelming. Amber attempts to change this by offering a zero-interaction security system, which will use the honeypot approach of decision through Presence (DtP) to generate a blacklist of third parties, which can be passed on to a network enforcer. Empirical testing has proved the usefulness of this alternative and low cost approach in defending networks. The functionality of the system was also extended by installing nodes in different geographical locations, and streaming their detections into the central Amber hive.
- Full Text:
- Date Issued: 2015
- Authors: Schoeman, Adam
- Date: 2015
- Subjects: Security systems -- Security measures , Computer viruses , Intrusion detection systems (Computer security) , Computer security
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4716 , http://hdl.handle.net/10962/d1017938
- Description: For the greater part, security controls are based on the principle of Decision through Detection (DtD). The exception to this is a honeypot, which analyses interactions between a third party and itself, while occupying a piece of unused information space. As honeypots are not located on productive information resources, any interaction with it can be assumed to be non-productive. This allows the honeypot to make decisions based simply on the presence of data, rather than on the behaviour of the data. But due to limited resources in human capital, honeypots’ uptake in the South African market has been underwhelming. Amber attempts to change this by offering a zero-interaction security system, which will use the honeypot approach of decision through Presence (DtP) to generate a blacklist of third parties, which can be passed on to a network enforcer. Empirical testing has proved the usefulness of this alternative and low cost approach in defending networks. The functionality of the system was also extended by installing nodes in different geographical locations, and streaming their detections into the central Amber hive.
- Full Text:
- Date Issued: 2015
Within- and between-beach variation in intertidal macrofaunal communities inhabiting two Transkei sandy beaches
- Authors: Dreyer, Nicolaas Burger
- Date: 2008
- Subjects: Intertidal animals -- Ecology -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10700 , http://hdl.handle.net/10948/1070 , Intertidal animals -- Ecology -- South Africa
- Description: Until recently most sandy beach studies have made use of snapshot samples but the validity of this approach has been widely questioned. In this study we attempt to resolve this issue by repeatedly sampling two beaches using a stratified random design. Three sampling sessions took place, each approximately six months apart. The three sites on the first beach were selected according to the type of beach (reflective, intermediate and dissipative) with each morphological type duplicated on the second beach. Many of the physical variables measured had significant differences between the sampling sessions but only a few were significantly different between the Sites. Very few of the individual physical variables had significant relationships with the sandy beach macrofaunal abundance and density. However, composite indices had a greater number of significant relationships with the macrofaunal abundance and density. Also very few significant relationships were seen between the species richness and the physical variables of the beaches studied. Effluent line crossing frequency was the only physical variable that could predict species richness but it was considered a weak predictor. Changes in the zonation patterns within and between beaches were also investigated. The highest concentration of taxa and individuals was found near the low-water mark with a gradual reduction of both towards the high-water mark. Some of the sandy beach community variables (abundance, density and species richness) showed significant difference between the sampling sessions but no significant differences were seen between the two beaches. The presence of three zones was noted using MDS plots and Cluster diagrams. However, using a SIMPER analyses, four zones with the possibility of a fifth was noted.
- Full Text:
- Date Issued: 2008
- Authors: Dreyer, Nicolaas Burger
- Date: 2008
- Subjects: Intertidal animals -- Ecology -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10700 , http://hdl.handle.net/10948/1070 , Intertidal animals -- Ecology -- South Africa
- Description: Until recently most sandy beach studies have made use of snapshot samples but the validity of this approach has been widely questioned. In this study we attempt to resolve this issue by repeatedly sampling two beaches using a stratified random design. Three sampling sessions took place, each approximately six months apart. The three sites on the first beach were selected according to the type of beach (reflective, intermediate and dissipative) with each morphological type duplicated on the second beach. Many of the physical variables measured had significant differences between the sampling sessions but only a few were significantly different between the Sites. Very few of the individual physical variables had significant relationships with the sandy beach macrofaunal abundance and density. However, composite indices had a greater number of significant relationships with the macrofaunal abundance and density. Also very few significant relationships were seen between the species richness and the physical variables of the beaches studied. Effluent line crossing frequency was the only physical variable that could predict species richness but it was considered a weak predictor. Changes in the zonation patterns within and between beaches were also investigated. The highest concentration of taxa and individuals was found near the low-water mark with a gradual reduction of both towards the high-water mark. Some of the sandy beach community variables (abundance, density and species richness) showed significant difference between the sampling sessions but no significant differences were seen between the two beaches. The presence of three zones was noted using MDS plots and Cluster diagrams. However, using a SIMPER analyses, four zones with the possibility of a fifth was noted.
- Full Text:
- Date Issued: 2008
Immunolocalisation of, and ultrastructural changes in the LH gonadotropes of Miniopterus schreibersii and Rhinolophus capensis (Mammalia: Chiroptera) in relation to their reproductive cycles
- Authors: Bojarski, Christina
- Date: 1990
- Subjects: Bats -- Reproduction
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5589 , http://hdl.handle.net/10962/d1002039
- Description: LH gonadotropes are successfully identified in the anterior pituitary of Minioptems schreibersii and Rhinolophus capensis, using immunogold labelling at the light and electron microscopy level. The gonadotropes are oval to polygonal in shape and possess numerous small secretory granules, which contain LH throughout the year. Their distribution is similar in both species, although the abundance varies slightly between species and sexes. Seasonal changes are detected in gonadotrope ultrastructure, pituitary LH levels, and plasma hormone levels, and activity pattern of LH gonadotropes generally coincide with reproductive activity in both bat species. In female M. schreibersii gonadotrope activity, pituitary LH, and plasma LH levels coincide with development, implantation and gestation. During the delayed implantation gonadotropes are inactive and and high follicular period of plasma LH levels are low, coinciding with corpus luteum inactivity and low plasma progesterone levels. Implantation coincides with increased activity of the gonadotrope activity, increased plasma LH levels, reactivation of the corpus luteum and elevated plasma progesterone levels. Activation of LH gonadotropes towards the end of hibernation may be initiated by the winter solstice, which marks the change to increasing daylength. In female R capensis gonadotrope activity and high pituitary and plasma LH levels occur towards the end of follicular development. During hibernation gonadotrope activity and plasma LH levels decrease. Ovulation coincides with increasing gonadotrope activity (which follows the winter solstice), although a preovulatory peak in plasma LH is not detected. In male M. schreibersii and R. capensis, gonadotrope activity and high plasma LH and testosterone levels coincide with spermatogenesis, except during a period of reproductive inactivity in spring in male M. schreibersii, where gonadotropes appear active and plasma LH and testosterone levels are high. The reason for this apparent activity is not known. Male sperm storage during hibernation in male R. capensis coincides with low gonadotrope activity and low plasma LH and testosterone levels. Factors initiating gonadotrope activity and hence spermatogenesis are probably decreasing daylength (summer solstice) in M. schreibersii and increasing ambient temperatures and food abundance (following the hibernation period) in R.capensis.
- Full Text:
- Date Issued: 1990
- Authors: Bojarski, Christina
- Date: 1990
- Subjects: Bats -- Reproduction
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5589 , http://hdl.handle.net/10962/d1002039
- Description: LH gonadotropes are successfully identified in the anterior pituitary of Minioptems schreibersii and Rhinolophus capensis, using immunogold labelling at the light and electron microscopy level. The gonadotropes are oval to polygonal in shape and possess numerous small secretory granules, which contain LH throughout the year. Their distribution is similar in both species, although the abundance varies slightly between species and sexes. Seasonal changes are detected in gonadotrope ultrastructure, pituitary LH levels, and plasma hormone levels, and activity pattern of LH gonadotropes generally coincide with reproductive activity in both bat species. In female M. schreibersii gonadotrope activity, pituitary LH, and plasma LH levels coincide with development, implantation and gestation. During the delayed implantation gonadotropes are inactive and and high follicular period of plasma LH levels are low, coinciding with corpus luteum inactivity and low plasma progesterone levels. Implantation coincides with increased activity of the gonadotrope activity, increased plasma LH levels, reactivation of the corpus luteum and elevated plasma progesterone levels. Activation of LH gonadotropes towards the end of hibernation may be initiated by the winter solstice, which marks the change to increasing daylength. In female R capensis gonadotrope activity and high pituitary and plasma LH levels occur towards the end of follicular development. During hibernation gonadotrope activity and plasma LH levels decrease. Ovulation coincides with increasing gonadotrope activity (which follows the winter solstice), although a preovulatory peak in plasma LH is not detected. In male M. schreibersii and R. capensis, gonadotrope activity and high plasma LH and testosterone levels coincide with spermatogenesis, except during a period of reproductive inactivity in spring in male M. schreibersii, where gonadotropes appear active and plasma LH and testosterone levels are high. The reason for this apparent activity is not known. Male sperm storage during hibernation in male R. capensis coincides with low gonadotrope activity and low plasma LH and testosterone levels. Factors initiating gonadotrope activity and hence spermatogenesis are probably decreasing daylength (summer solstice) in M. schreibersii and increasing ambient temperatures and food abundance (following the hibernation period) in R.capensis.
- Full Text:
- Date Issued: 1990
Synthetic and spectrometric investigation of 1,4-benzoxazepines
- Authors: Whittal, R D
- Date: 1990
- Subjects: Spectrum analysis , Benzodiazepines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4381 , http://hdl.handle.net/10962/d1005046
- Description: Flavanone (2,3-dihydro-2-phenyl-4H-benzopyran-4-one) and a series of 4'- and 7-halogeno derivatives were prepared from the corresponding 2'-hydroxychalcones [1-(2-hydroxyphenyl)-3-phenyl-2-propen-l-ones], which, in turn, were synthesized by aldol condensation of substituted 2'-hydroxacetophenones with various benzaldehydes. A series of 2,3-dihydro-2-phenyl-l,4-benzoxazepin-5(4H)-ones were prepared by ring expansion of the corresponding flavanones, via the Schmidt reaction, using trimethylsilylazide and trifluoroacetic acid. A series of tetrazoles {2,3-dihydro-2-phenyl-tetrazolo[1,5-d]-1,4-benzoxazepines} were also isolated as by-products of the Schmidt reaction. Flavanone oxime was synthesized for use in Beckmann reactions, and its molecular structure was determined by x-ray crystallography. Attempts to prepare 1,4-benzoxazepinone or its 1,5-analogue via Beckmann rearrangement of flavanone oxime, with polyphosphoric acid or phosphorus pentachloride catalysts, however, were unsuccessful. Several methods for introducing Δ²-unsaturation into the benzoxazepinone system were also examined. High resolution ¹H n.m.r., computer modelling, and molecular mechanics techniques were used to determine the conformations of the heterocycles of the benzoxazepinones and tetrazoles and results are compared with earlier studies in this field. Certain trends in the fragmentation patterns were observed in the low resolution mass spectra of the benzoxazepinones and tetrazoles, and high resolution mass spectrometric data were used to explore the major fragmentation patterns of these compounds.
- Full Text:
- Date Issued: 1990
- Authors: Whittal, R D
- Date: 1990
- Subjects: Spectrum analysis , Benzodiazepines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4381 , http://hdl.handle.net/10962/d1005046
- Description: Flavanone (2,3-dihydro-2-phenyl-4H-benzopyran-4-one) and a series of 4'- and 7-halogeno derivatives were prepared from the corresponding 2'-hydroxychalcones [1-(2-hydroxyphenyl)-3-phenyl-2-propen-l-ones], which, in turn, were synthesized by aldol condensation of substituted 2'-hydroxacetophenones with various benzaldehydes. A series of 2,3-dihydro-2-phenyl-l,4-benzoxazepin-5(4H)-ones were prepared by ring expansion of the corresponding flavanones, via the Schmidt reaction, using trimethylsilylazide and trifluoroacetic acid. A series of tetrazoles {2,3-dihydro-2-phenyl-tetrazolo[1,5-d]-1,4-benzoxazepines} were also isolated as by-products of the Schmidt reaction. Flavanone oxime was synthesized for use in Beckmann reactions, and its molecular structure was determined by x-ray crystallography. Attempts to prepare 1,4-benzoxazepinone or its 1,5-analogue via Beckmann rearrangement of flavanone oxime, with polyphosphoric acid or phosphorus pentachloride catalysts, however, were unsuccessful. Several methods for introducing Δ²-unsaturation into the benzoxazepinone system were also examined. High resolution ¹H n.m.r., computer modelling, and molecular mechanics techniques were used to determine the conformations of the heterocycles of the benzoxazepinones and tetrazoles and results are compared with earlier studies in this field. Certain trends in the fragmentation patterns were observed in the low resolution mass spectra of the benzoxazepinones and tetrazoles, and high resolution mass spectrometric data were used to explore the major fragmentation patterns of these compounds.
- Full Text:
- Date Issued: 1990
A review of the economic geology of tungsten
- Authors: Bowles, Michael
- Date: 1979
- Subjects: Tungsten Geology, Economic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4897 , http://hdl.handle.net/10962/d1001556
- Description: A description of the geochemistry of tungsten is given. The geochemical properties of tungsten have a strong influence on its mineralogy, distribution and abundance in crustal rocks and rock-forming minerals , and its migration/deposition within the ore-forming and supergene environments. The behaviour of tungsten during migration, from source to site of deposition, within the crust is discussed in some detail and environments considered favourable to the concentration of tungsten ore minerals are suggested. All major types of tungsten ore deposit are described with emphasis placed on those of greater economic importance. Characteristic features of each type of deposit are particularly emphasized in order to provide clear guidelines to exploration. Hydrothermal, pyrometasomatic and stratabound tungsten deposits present themselves, economically, as the most important exploration targets. The recently developed concept of syngenetic stratabound tungsten mineralisation is outlined. Exploration for deposits of this type should be aimed predominantly, but not exclusively, at volcano-sedimentary sequences of Lower Palaeozoic age, particularly within regions known to contain occurrences of Sb and Hg. Tungsten deposits commonly contain concentrations of one or more of the following metals: Sn, Sb, Bi, Mo, Au and Ag. The presence and possible extractive value of these metals, together with commonly associated metal impurities such as As, must always be taken into account in a feasibility study , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 1979
- Authors: Bowles, Michael
- Date: 1979
- Subjects: Tungsten Geology, Economic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4897 , http://hdl.handle.net/10962/d1001556
- Description: A description of the geochemistry of tungsten is given. The geochemical properties of tungsten have a strong influence on its mineralogy, distribution and abundance in crustal rocks and rock-forming minerals , and its migration/deposition within the ore-forming and supergene environments. The behaviour of tungsten during migration, from source to site of deposition, within the crust is discussed in some detail and environments considered favourable to the concentration of tungsten ore minerals are suggested. All major types of tungsten ore deposit are described with emphasis placed on those of greater economic importance. Characteristic features of each type of deposit are particularly emphasized in order to provide clear guidelines to exploration. Hydrothermal, pyrometasomatic and stratabound tungsten deposits present themselves, economically, as the most important exploration targets. The recently developed concept of syngenetic stratabound tungsten mineralisation is outlined. Exploration for deposits of this type should be aimed predominantly, but not exclusively, at volcano-sedimentary sequences of Lower Palaeozoic age, particularly within regions known to contain occurrences of Sb and Hg. Tungsten deposits commonly contain concentrations of one or more of the following metals: Sn, Sb, Bi, Mo, Au and Ag. The presence and possible extractive value of these metals, together with commonly associated metal impurities such as As, must always be taken into account in a feasibility study , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 1979
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