Agreement and coordination in XiTsonga, SeSotho and IsiXhosa: an optimality theoretic perspective
- Authors: Mitchley, Hazel
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/3423 , vital:20491
- Description: This thesis provides a unified Optimality Theoretic analysis of subject-verb agreement with coordinated preverbal subjects in three Southern Bantu languages: Xitsonga (S53), Sesotho (S33), and isiXhosa (S41). This analysis is then used to formulate a typology of agreement resolution strategies and the contexts which trigger them. Although some accounts in the Bantu literature suggest that agreement with coordinate structures is avoided by speakers (e.g. Schadeberg 1992, Voeltz 1971) especially when conjuncts are from different noun classes, I show that there is ample evidence to the contrary, and that the subject marker used is dependent on several factors, including (i) the [-HUMAN] specification on the conjuncts, (ii) whether the conjuncts are singular or plural, (iii) whether or not the conjuncts both carry the same noun class feature, and (iv) the order of the conjuncts. This thesis shows that there are various agreement resolution strategies which can beused: 1) agreement with the [+HUMAN] feature on the conjuncts, 2) agreement with the[-HUMAN] feature on the conjuncts, 3) agreement with the noun class feature on both conjuncts, 4) agreement with the noun class feature on the conjunct closest to the verb, and 5) agreement with the noun class feature on the conjunct furthest from the verb. Not all of these strategies are used by all languages, nor are these strategies interchangeable in the languages which do use them – instead, multiple factors conspire to trigger the use of a specific agreement strategy within a specific agreement featural context. I show that these effects can be captured using Optimality Theory (Prince and Smolensky 2004). The analysis makes use of seven constraints: RES#, MAX[+H], MAX[-H], DEP[-H], MAXNC, DEPNC, and AGREECLOSEST. The hierarchical ranking of these constraints not only accounts for the confinement of particular strategies to specific agreement featural contexts within a language, but also accounts for the cross-linguistic differences in the use of these strategies. I end off by examining the typological implications which follow from the OT analysis provided in this thesis.
- Full Text:
- Date Issued: 2016
- Authors: Mitchley, Hazel
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/3423 , vital:20491
- Description: This thesis provides a unified Optimality Theoretic analysis of subject-verb agreement with coordinated preverbal subjects in three Southern Bantu languages: Xitsonga (S53), Sesotho (S33), and isiXhosa (S41). This analysis is then used to formulate a typology of agreement resolution strategies and the contexts which trigger them. Although some accounts in the Bantu literature suggest that agreement with coordinate structures is avoided by speakers (e.g. Schadeberg 1992, Voeltz 1971) especially when conjuncts are from different noun classes, I show that there is ample evidence to the contrary, and that the subject marker used is dependent on several factors, including (i) the [-HUMAN] specification on the conjuncts, (ii) whether the conjuncts are singular or plural, (iii) whether or not the conjuncts both carry the same noun class feature, and (iv) the order of the conjuncts. This thesis shows that there are various agreement resolution strategies which can beused: 1) agreement with the [+HUMAN] feature on the conjuncts, 2) agreement with the[-HUMAN] feature on the conjuncts, 3) agreement with the noun class feature on both conjuncts, 4) agreement with the noun class feature on the conjunct closest to the verb, and 5) agreement with the noun class feature on the conjunct furthest from the verb. Not all of these strategies are used by all languages, nor are these strategies interchangeable in the languages which do use them – instead, multiple factors conspire to trigger the use of a specific agreement strategy within a specific agreement featural context. I show that these effects can be captured using Optimality Theory (Prince and Smolensky 2004). The analysis makes use of seven constraints: RES#, MAX[+H], MAX[-H], DEP[-H], MAXNC, DEPNC, and AGREECLOSEST. The hierarchical ranking of these constraints not only accounts for the confinement of particular strategies to specific agreement featural contexts within a language, but also accounts for the cross-linguistic differences in the use of these strategies. I end off by examining the typological implications which follow from the OT analysis provided in this thesis.
- Full Text:
- Date Issued: 2016
Fungal remediation of winery and distillery wastewaters using Trametes pubescens MB 89 and the enhanced production of a high-value enzyme therein
- Authors: Strong, Peter James
- Date: 2008
- Subjects: Fungal remediation Distilleries -- Waste disposal Wine and wine making -- Waste disposal Bioremediation Laccase Enzymes -- Biotechnology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3932 , http://hdl.handle.net/10962/d1003991
- Description: In this study white-rot fungi were investigated for their efficiency at distillery wastewater remediation and the production of laccase as a valuable by-product. Distillery wastewaters are high in organic load and low in pH. The presence of phenolic compounds can lead to extremely colour-rich wastewaters and can be toxic to microorganisms. The presence of the inorganic ions may also affect biological treatment. White-rot fungi are unique among eukaryotic or prokaryotic microbes in possessing powerful oxidative enzyme systems that can degrade lignin to carbon dioxide. These ligninolytic enzymes, such as lignin peroxidase, manganese peroxidase and laccase, are capable of degrading a vast range of toxic, recalcitrant environmental pollutants and this makes the white-rot fungi strong candidates for the bioremediation of polluted soils and waters. The laccase enzyme alone has shown remediation potential in wastewaters such as beer production effluent, olive mill wastewater, alcohol distillery wastes, dye-containing wastewaters from the textile industry as well as wastewaters from the paper and pulp industry. It has been shown to be capable of remediating soils and waters polluted with chlorinated phenolic compounds, polyaromatic hydrocarbons, nitrosubstituted compounds and fungicides, herbicides and insecticides.
- Full Text:
- Date Issued: 2008
- Authors: Strong, Peter James
- Date: 2008
- Subjects: Fungal remediation Distilleries -- Waste disposal Wine and wine making -- Waste disposal Bioremediation Laccase Enzymes -- Biotechnology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3932 , http://hdl.handle.net/10962/d1003991
- Description: In this study white-rot fungi were investigated for their efficiency at distillery wastewater remediation and the production of laccase as a valuable by-product. Distillery wastewaters are high in organic load and low in pH. The presence of phenolic compounds can lead to extremely colour-rich wastewaters and can be toxic to microorganisms. The presence of the inorganic ions may also affect biological treatment. White-rot fungi are unique among eukaryotic or prokaryotic microbes in possessing powerful oxidative enzyme systems that can degrade lignin to carbon dioxide. These ligninolytic enzymes, such as lignin peroxidase, manganese peroxidase and laccase, are capable of degrading a vast range of toxic, recalcitrant environmental pollutants and this makes the white-rot fungi strong candidates for the bioremediation of polluted soils and waters. The laccase enzyme alone has shown remediation potential in wastewaters such as beer production effluent, olive mill wastewater, alcohol distillery wastes, dye-containing wastewaters from the textile industry as well as wastewaters from the paper and pulp industry. It has been shown to be capable of remediating soils and waters polluted with chlorinated phenolic compounds, polyaromatic hydrocarbons, nitrosubstituted compounds and fungicides, herbicides and insecticides.
- Full Text:
- Date Issued: 2008
Studies in carangid fishes no. 4: the identity of Scomber Sansun Forsskal, 1775
- Smith, J.L.B. (James Leonard Brierley), 1897-1968
- Authors: Smith, J.L.B. (James Leonard Brierley), 1897-1968
- Date: 1986
- Language: English
- Type: Text
- Identifier: vital:15050 , http://hdl.handle.net/10962/d1020232
- Full Text:
- Date Issued: 1986
- Authors: Smith, J.L.B. (James Leonard Brierley), 1897-1968
- Date: 1986
- Language: English
- Type: Text
- Identifier: vital:15050 , http://hdl.handle.net/10962/d1020232
- Full Text:
- Date Issued: 1986
The use of Landsat ETM imagery as a suitable data capture source for alien acacia species for the WFW programme
- Authors: Cobbing, Benedict Louis
- Date: 2007
- Subjects: Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4856 , http://hdl.handle.net/10962/d1005532 , Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Description: Geographic Information System technology today allows for the rapid analysis of vast amounts of spatial and non-spatial data. The power of a GIS can only be effected with the rapid collection of accurate input data. This is particularly true in the case of the South African National Working for Water (WFW) Programme where large volumes of spatial data on alien vegetation infestations are captured throughout the country. Alien vegetation clearing contracts cannot be generated, for WFW, without this data, so that the accurate capture of such data is crucial to the success of the programme. Mapping Invasive Alien Plant (IAP) data within WFW is a perennial problem (Coetzee, pers com, 2002), because not enough mapping is being done to meet the annual requirements of the programme in the various provinces. This is re-iterated by Richardson, 2004, who states that there is a shortage of accurate data on IAP abundance in South Africa. Therefore there is a need to investigate alternate methods of data capture; such as remote sensing, whilst working within the existing WFW data capture standards. The aim of this research was to investigate the use of Landsat ETM imagery as a data capture source for mapping alien vegetation for the WFW Programme in terms of their approved mapping methods, for both automated and manual classification techniques. The automated and manual classification results were compared to control data captured by differential Global Positioning Systems (DGPS). The research tested the various methods of data capture using Landsat ETM images over a range of study sites of varying complexity: a simple grassland area, a medium complexity grassy fynbos site and a complicated indigenous forest site. An important component of the research was to develop a mapping (classification) Ranking System based upon variables identified by WFW as fundamental in data capture decision making: spatial and positional accuracy, time constraints and cost constraints for three typical alien invaded areas. The mapping Ranking System compared the results of the various mapping methods for each factor for the study sites against each other. This provided an indication of which mapping method is the most efficient or suitable for a particular area.
- Full Text:
- Date Issued: 2007
- Authors: Cobbing, Benedict Louis
- Date: 2007
- Subjects: Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4856 , http://hdl.handle.net/10962/d1005532 , Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Description: Geographic Information System technology today allows for the rapid analysis of vast amounts of spatial and non-spatial data. The power of a GIS can only be effected with the rapid collection of accurate input data. This is particularly true in the case of the South African National Working for Water (WFW) Programme where large volumes of spatial data on alien vegetation infestations are captured throughout the country. Alien vegetation clearing contracts cannot be generated, for WFW, without this data, so that the accurate capture of such data is crucial to the success of the programme. Mapping Invasive Alien Plant (IAP) data within WFW is a perennial problem (Coetzee, pers com, 2002), because not enough mapping is being done to meet the annual requirements of the programme in the various provinces. This is re-iterated by Richardson, 2004, who states that there is a shortage of accurate data on IAP abundance in South Africa. Therefore there is a need to investigate alternate methods of data capture; such as remote sensing, whilst working within the existing WFW data capture standards. The aim of this research was to investigate the use of Landsat ETM imagery as a data capture source for mapping alien vegetation for the WFW Programme in terms of their approved mapping methods, for both automated and manual classification techniques. The automated and manual classification results were compared to control data captured by differential Global Positioning Systems (DGPS). The research tested the various methods of data capture using Landsat ETM images over a range of study sites of varying complexity: a simple grassland area, a medium complexity grassy fynbos site and a complicated indigenous forest site. An important component of the research was to develop a mapping (classification) Ranking System based upon variables identified by WFW as fundamental in data capture decision making: spatial and positional accuracy, time constraints and cost constraints for three typical alien invaded areas. The mapping Ranking System compared the results of the various mapping methods for each factor for the study sites against each other. This provided an indication of which mapping method is the most efficient or suitable for a particular area.
- Full Text:
- Date Issued: 2007
Diet of the yellow mongoose (Cynictis penicillata) in the Albany Thicket Biome of South Africa
- Authors: Bizani, Mfundo
- Date: 2014
- Language: English
- Type: Thesis , Masters , MSc (Zoology)
- Identifier: vital:11796 , http://hdl.handle.net/10353/d1019840
- Description: The dietary habits of the yellow mongoose Cynictis penicillata were studied in the Albany Thicket Biome of South Africa (Great Fish River Reserve, Eastern Cape). The diet was investigated through the analysis of 1,056 scats that were sampled over a period of 7 years (2005−2009 and 2011−2012) mainly in three similar sites (Kelarny, Grasslands and Junction 10) that were used by at least three families or groups of yellow mongooses. Scats were collected near latrine sites, labelled and stored in a freezer. In the laboratory, scats were oven dried for a period of 24 hours at 50 C. Diet was determined by identifying undigested food remains in the scats. Hair samples were examined under the compound microscope to identify which mammals were ingested. In the field, both arthropod and small mammal abundance were determined in order to evaluate whether yellow mongooses are opportunistic or specialist feeders. Furthermore, inter-annual (2006–2008) and inter-group/inter-site variations in the diet were assessed. Based on faecal analysis, arthropods were the principal prey, while small mammals acted as supplementary food item. Other food categories like vegetation, reptiles and birds were only ingested or preyed upon infrequently. Intermediate dietary diversity, and low standardised diet breadth indices were obtained for all seasons, as well as for the whole sampling period. The diet overlaps calculated for pairs of seasons were very high and did not differ substantially. However, the diet of the yellow mongoose varied seasonally, yearly and between groups (sites), mostly due to variations in arthropod and small mammal consumption. Food availability displayed an increase in biomass of both small mammals and arthropods in summer and autumn. Results obtained in this study could suggest that the yellow mongoose at the GFRR is insectivorous by preferring to feed on insects (and arthropods in general) when both insects and rodents are abundant. However the fact that its diet varies both seasonally, yearly and locally, as well as the presence of remains of other food categories in the scats, indicates that this species is rather an opportunistic, generalist feeder than an insect specialist.
- Full Text:
- Date Issued: 2014
- Authors: Bizani, Mfundo
- Date: 2014
- Language: English
- Type: Thesis , Masters , MSc (Zoology)
- Identifier: vital:11796 , http://hdl.handle.net/10353/d1019840
- Description: The dietary habits of the yellow mongoose Cynictis penicillata were studied in the Albany Thicket Biome of South Africa (Great Fish River Reserve, Eastern Cape). The diet was investigated through the analysis of 1,056 scats that were sampled over a period of 7 years (2005−2009 and 2011−2012) mainly in three similar sites (Kelarny, Grasslands and Junction 10) that were used by at least three families or groups of yellow mongooses. Scats were collected near latrine sites, labelled and stored in a freezer. In the laboratory, scats were oven dried for a period of 24 hours at 50 C. Diet was determined by identifying undigested food remains in the scats. Hair samples were examined under the compound microscope to identify which mammals were ingested. In the field, both arthropod and small mammal abundance were determined in order to evaluate whether yellow mongooses are opportunistic or specialist feeders. Furthermore, inter-annual (2006–2008) and inter-group/inter-site variations in the diet were assessed. Based on faecal analysis, arthropods were the principal prey, while small mammals acted as supplementary food item. Other food categories like vegetation, reptiles and birds were only ingested or preyed upon infrequently. Intermediate dietary diversity, and low standardised diet breadth indices were obtained for all seasons, as well as for the whole sampling period. The diet overlaps calculated for pairs of seasons were very high and did not differ substantially. However, the diet of the yellow mongoose varied seasonally, yearly and between groups (sites), mostly due to variations in arthropod and small mammal consumption. Food availability displayed an increase in biomass of both small mammals and arthropods in summer and autumn. Results obtained in this study could suggest that the yellow mongoose at the GFRR is insectivorous by preferring to feed on insects (and arthropods in general) when both insects and rodents are abundant. However the fact that its diet varies both seasonally, yearly and locally, as well as the presence of remains of other food categories in the scats, indicates that this species is rather an opportunistic, generalist feeder than an insect specialist.
- Full Text:
- Date Issued: 2014
Studies in Carangid fishes no 6: key to western Indian Ocean species of the genus Carangoides Bleeker, 1851, with a desciption of Carangoides Nitidus Smith
- Authors: Smith, Margaret Mary
- Date: 1972
- Language: English
- Type: Text
- Identifier: vital:15053 , http://hdl.handle.net/10962/d1020235
- Full Text:
- Date Issued: 1972
- Authors: Smith, Margaret Mary
- Date: 1972
- Language: English
- Type: Text
- Identifier: vital:15053 , http://hdl.handle.net/10962/d1020235
- Full Text:
- Date Issued: 1972
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
Screening of technologies for the recovery of rhodium (III) metal ions from a precious metal refinery wastewater
- Authors: Mack, Cherie-Lynn
- Date: 2005
- Subjects: Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3987 , http://hdl.handle.net/10962/d1004046 , Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Description: The selective recovery of rhodium from wastewaters, in which the metal would be otherwise lost, would be highly profitable if the process were suitably low-cost. Current recovery processes are generally high maintenance and high-cost, whereas biological processes can be engineered to run with little external input in terms of cost and maintenance. Three emerging technologies were chosen based on their reported efficiency when removing base metals from wastewaters. The first technology screened, the sulphide-extraction membrane bioreactor (SEMB), consists of a sulphate-reducing prokaryote (SRP) anaerobic digester, in which a silicone membrane is submerged. Wastewater is passed through the membrane and metal ions are precipitated as metal sulphides by the hydrogen sulphide gas, which is capable of permeating the membrane. The second technology screened was a fluidized sand bed reactor in which metal ions are removed from solution via induction of nucleated precipitation by sodium carbonate onto the sand grains. The third, and most well established removal technology screened was a biosorption system using immobilized Saccharomyces cerevisiae biomass as the biosorbent. Experimental trials with each technology highlighted drawbacks with each; the SEMB system proved to be largely ineffective when challenged with the removal of rhodium from the wastewater as the rhodium precipitate fouled the membrane within hours, the fluidized bed system seemed unable to overcome the acidity of the wastewater and thus could not precipitate out the rhodium metal, and the efficiency of the biosorption process was hampered by the diversity of rhodium species present in the wastewater, which reduced the amount recovered. The outcomes of the trials with each technology indicated that further optimization of the technology or pretreatment of the wastewater is necessary before any of these options can be implemented. It could be concluded, however, that despite further optimization, both the SEMB and the fluidized bed system were not applicable in this case as precipitation would be non-specific, resulting in the necessity for further steps in order to purify the rhodium ions. Hence, the biosorption system was shown to be most applicable, and further optimization of the system could yield a highly efficient rhodium recovery process.
- Full Text:
- Date Issued: 2005
- Authors: Mack, Cherie-Lynn
- Date: 2005
- Subjects: Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3987 , http://hdl.handle.net/10962/d1004046 , Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Description: The selective recovery of rhodium from wastewaters, in which the metal would be otherwise lost, would be highly profitable if the process were suitably low-cost. Current recovery processes are generally high maintenance and high-cost, whereas biological processes can be engineered to run with little external input in terms of cost and maintenance. Three emerging technologies were chosen based on their reported efficiency when removing base metals from wastewaters. The first technology screened, the sulphide-extraction membrane bioreactor (SEMB), consists of a sulphate-reducing prokaryote (SRP) anaerobic digester, in which a silicone membrane is submerged. Wastewater is passed through the membrane and metal ions are precipitated as metal sulphides by the hydrogen sulphide gas, which is capable of permeating the membrane. The second technology screened was a fluidized sand bed reactor in which metal ions are removed from solution via induction of nucleated precipitation by sodium carbonate onto the sand grains. The third, and most well established removal technology screened was a biosorption system using immobilized Saccharomyces cerevisiae biomass as the biosorbent. Experimental trials with each technology highlighted drawbacks with each; the SEMB system proved to be largely ineffective when challenged with the removal of rhodium from the wastewater as the rhodium precipitate fouled the membrane within hours, the fluidized bed system seemed unable to overcome the acidity of the wastewater and thus could not precipitate out the rhodium metal, and the efficiency of the biosorption process was hampered by the diversity of rhodium species present in the wastewater, which reduced the amount recovered. The outcomes of the trials with each technology indicated that further optimization of the technology or pretreatment of the wastewater is necessary before any of these options can be implemented. It could be concluded, however, that despite further optimization, both the SEMB and the fluidized bed system were not applicable in this case as precipitation would be non-specific, resulting in the necessity for further steps in order to purify the rhodium ions. Hence, the biosorption system was shown to be most applicable, and further optimization of the system could yield a highly efficient rhodium recovery process.
- Full Text:
- Date Issued: 2005
Learners' perceptions of creating a collaborative hypermedia product: an exploratory case study at Mount Pleasant Primary School
- Authors: du Plessis, André
- Date: 2004
- Subjects: Computer-assisted instruction -- South Africa Computers -- Study and teaching -- South Africa Education, Elementary -- Activity programs Competency-based education -- South Africa Educational technology -- South Africa
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1663 , http://hdl.handle.net/10962/d1003546
- Description: The Ministry of Education (SICTE, 2002) states that the widespread introduction of computers in schools should support Curriculum 2005 and that computer technology is part and parcel of making schools the center of community life. The vision is to establish Smart Schools: schools that are reinvented in terms of teaching-learning practices to prepare learners for the information era (SICTE, 2002). Kafai (1996:71) has found that conventional school assignments rarely give learners the opportunity to spend a great deal of time on complex projects. As a result, many learners have little experience in design: planning, problem solving, researching, dealing with time constraints, modifying expectations and synthesizing everything in a project. Research by Carver, Lehrer, Connell and Erickson (1992); Lehrer, (1993); Lehrer, Erickson and Connell (1994); Kafai (1996); Liu and Hsiao (2002) and Liu (2002) indicates that the design of hypermedia artefacts can assist in providing experience in design. To date, no equivalent research has been conducted in South Africa to ascertain the perceptions of learners regarding the creation of a hypermedia artefact over an extended period of time and whether some of the critical outcomes specified in Curriculum 2005 can be addressed in such a learning-by-design hypermedia project. This study shows that design skills and aspects related to the critical outcomes of Curriculum 2005 can be achieved. Furthermore, it indicates that this kind of project encourages interest, motivation and collaboration. In addition, it suggests that learners experience the role of the teacher as different and prefer such a learning environment. In spite of the positive results, some aspects that need attention for future implementation are suggested.
- Full Text:
- Date Issued: 2004
- Authors: du Plessis, André
- Date: 2004
- Subjects: Computer-assisted instruction -- South Africa Computers -- Study and teaching -- South Africa Education, Elementary -- Activity programs Competency-based education -- South Africa Educational technology -- South Africa
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1663 , http://hdl.handle.net/10962/d1003546
- Description: The Ministry of Education (SICTE, 2002) states that the widespread introduction of computers in schools should support Curriculum 2005 and that computer technology is part and parcel of making schools the center of community life. The vision is to establish Smart Schools: schools that are reinvented in terms of teaching-learning practices to prepare learners for the information era (SICTE, 2002). Kafai (1996:71) has found that conventional school assignments rarely give learners the opportunity to spend a great deal of time on complex projects. As a result, many learners have little experience in design: planning, problem solving, researching, dealing with time constraints, modifying expectations and synthesizing everything in a project. Research by Carver, Lehrer, Connell and Erickson (1992); Lehrer, (1993); Lehrer, Erickson and Connell (1994); Kafai (1996); Liu and Hsiao (2002) and Liu (2002) indicates that the design of hypermedia artefacts can assist in providing experience in design. To date, no equivalent research has been conducted in South Africa to ascertain the perceptions of learners regarding the creation of a hypermedia artefact over an extended period of time and whether some of the critical outcomes specified in Curriculum 2005 can be addressed in such a learning-by-design hypermedia project. This study shows that design skills and aspects related to the critical outcomes of Curriculum 2005 can be achieved. Furthermore, it indicates that this kind of project encourages interest, motivation and collaboration. In addition, it suggests that learners experience the role of the teacher as different and prefer such a learning environment. In spite of the positive results, some aspects that need attention for future implementation are suggested.
- Full Text:
- Date Issued: 2004
Studies in carangid fishes no. 2: the identity of Scomber Malabaricus Bloch-Schneider, 1801
- Smith, J.L.B. (James Leonard Brierley), 1897-1968
- Authors: Smith, J.L.B. (James Leonard Brierley), 1897-1968
- Date: 1967
- Language: English
- Type: Text
- Identifier: vital:15048 , http://hdl.handle.net/10962/d1020230
- Full Text:
- Date Issued: 1967
- Authors: Smith, J.L.B. (James Leonard Brierley), 1897-1968
- Date: 1967
- Language: English
- Type: Text
- Identifier: vital:15048 , http://hdl.handle.net/10962/d1020230
- Full Text:
- Date Issued: 1967
Altruistic love culture and workers well-being: a study in workplace spirituality
- Authors: Simms, Michelle
- Date: 2019
- Subjects: Employee assistance programs -- South Africa , Religion in the workplace Altruism Interpersonal relations and culture -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: http://hdl.handle.net/10948/43468 , vital:36892
- Description: Business leaders and company analysts identify the fact that the marketplace necessitates flexibility and mobility to triumph over the competitive difficulties which businesses usually encounter. More recently approaches have focused on the role that people perform in bringing about competitive advantage and in particular strategies on how to increase Employee Well-being. Given the need for Employee Well-being in order to achieve desired work-related results, management has become progressively more enthusiastic about methods to improve the well-being of their employees. This research study seeks to make a contribution to this topic by investigating how Employee Well-being can be increased by inculcating an Altruistic Love culture amongst employees. To achieve this objective an Employee Well-Being Model was presented. Spiritual Leadership in the workplace was discussed as the theoretical framework with Altruistic Love as a feature in the intrinsic model of motivation explained further. Six values were defined and according to the theoretical framework were important in order to achieve Employee Well-being. These values were Appreciation, Kindness, Integrity, Compassion, Humility and Forgiveness. The Employee Well-Being Model served as a basis for the compilation of the survey questionnaire to investigate the role of Altruistic Love values in achieving Employee Well-being. The questionnaire was administered in two stages. The first was a printed survey distributed to all workers at a FMCG company called Springbok Discount Meat Centre. The second part was an electronic survey sent out by email, where a link to the online survey could be accessed. The empirical results revealed that Appreciation, Kindness, Integrity and Humility were significantly positively related to Employee Well-being. Compassion was significantly negatively related to Employee Well-being. It can consequently be postulated that there will be a significant improvement of Employee Well-Being in the workplace if Altruistic Love values, defined in the study as Appreciation, Kindness, Integrity and Humility are practised more often by employees including management.
- Full Text:
- Date Issued: 2019
- Authors: Simms, Michelle
- Date: 2019
- Subjects: Employee assistance programs -- South Africa , Religion in the workplace Altruism Interpersonal relations and culture -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: http://hdl.handle.net/10948/43468 , vital:36892
- Description: Business leaders and company analysts identify the fact that the marketplace necessitates flexibility and mobility to triumph over the competitive difficulties which businesses usually encounter. More recently approaches have focused on the role that people perform in bringing about competitive advantage and in particular strategies on how to increase Employee Well-being. Given the need for Employee Well-being in order to achieve desired work-related results, management has become progressively more enthusiastic about methods to improve the well-being of their employees. This research study seeks to make a contribution to this topic by investigating how Employee Well-being can be increased by inculcating an Altruistic Love culture amongst employees. To achieve this objective an Employee Well-Being Model was presented. Spiritual Leadership in the workplace was discussed as the theoretical framework with Altruistic Love as a feature in the intrinsic model of motivation explained further. Six values were defined and according to the theoretical framework were important in order to achieve Employee Well-being. These values were Appreciation, Kindness, Integrity, Compassion, Humility and Forgiveness. The Employee Well-Being Model served as a basis for the compilation of the survey questionnaire to investigate the role of Altruistic Love values in achieving Employee Well-being. The questionnaire was administered in two stages. The first was a printed survey distributed to all workers at a FMCG company called Springbok Discount Meat Centre. The second part was an electronic survey sent out by email, where a link to the online survey could be accessed. The empirical results revealed that Appreciation, Kindness, Integrity and Humility were significantly positively related to Employee Well-being. Compassion was significantly negatively related to Employee Well-being. It can consequently be postulated that there will be a significant improvement of Employee Well-Being in the workplace if Altruistic Love values, defined in the study as Appreciation, Kindness, Integrity and Humility are practised more often by employees including management.
- Full Text:
- Date Issued: 2019
Synthesis and characterisation of lanthanide complexes with nitrogen- and oxygen-donor ligands
- Authors: Madanhire, Tatenda
- Date: 2016
- Subjects: Rare earth metals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/13127 , vital:27154
- Description: The reactions of Ln(NO3)3∙6H2O (Ln = Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H2pydm) were investigated, and complexes with the formula, [Ln(H2pydm)2(NO3)2](NO3) (Ln = Pr or Nd) and [Er(H2pydm)3](NO3)3 were isolated. The ten-coordinate Pr(III) and Nd(III) compounds crystallise in the triclinic space group P-1 while the nine-coordinate Er(III) complex crystallises in the monoclinic system (P21/n). The reaction of PrCl3∙6H2O with H2pydm yielded the compound, [Pr(H2pydm)3](Cl)3, that crystallises in the monoclinic system, space group P21/c with α = 90, β = 98.680(1) and γ = 90°. The nine-coordinate Pr(III) ion is bound to three H2pydm ligands, with bond distances Pr-O 2.455(2)-2.478(2) Å and Pr-N 2.6355(19)-2.64(2) Å. X-ray crystal structures of all the H2pydm complexes reveal that the ligand coordinates tridentately, via the pyridyl nitrogen atom and the two hydroxyl oxygen atoms. The electronic absorption spectra of complexes show 4f-4f transitions. Rare-earth complexes, [Ln(H2L1)2(NO3)3] [Ln = Gd, Ho or Nd], were also prepared from a Schiff base. The X-ray single-crystal diffraction studies and SHAPE analyses of the Gd(III) and Ho(III) complexes shows that the complexes are ten-coordinate and exhibit distorted tetradecahedron geometries. With proton migration occurring from the phenol group to the imine function, complexation of the lanthanides to the ligand gives the ligand a zwitterionic phenoxo-iminium form. A phenolate oxygen-bridged dinuclear complex, [Ce2(H2L1)(ovan)3(NO3)3], has been obtained by reacting Ce(NO3)3∙6H2O with an o-vanillin derived Schiff base ligand, 2-((E)-(1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (H2L1). Hydrolysis of the Schiff base occurred to yield o-vanillin, which bridged two cerium atoms with the Ce∙∙∙Ce distance equal to 3.823 Å. The Ce(III) ions are both tencoordinate, but have different coordination environments, showing tetradecahedron and staggered dodecahedron geometries, respectively. The reaction of salicylaldehyde-N(4)-diethylthiosemicarbazone (H2L2) in the presence of hydrated Ln(III) nitrates led to the isolation of two novel compounds: (E)-2[(ortho-hydroxy)benzylidene]-2-(thiomethyl)-thionohydrazide (1) and bis[2,3-diaza4-(2-hydroxyphenyl)-1-thiomethyl-buta-1,3-diene]disulfide. The latter is a dimer of the former. For this asymmetric Schiff base, 1 and the symmetric disulfide, classical hydrogen bonds of the O–H∙∙∙N as well as N–H∙∙∙S (for 1) type are apparent next to C–H∙∙∙O contacts. 4-(4-Bromophenyl)-1-(propan-2-ylidene)thiosemicarbazide was also prepared upon reacting 4-(4-bromophenyl)-3-thiosemicarbazide with acetone in the presence of ethanol and La(NO3)3∙6H2O. The C=S bond length was found to be 1.6686(16) Å which is in good agreement with other thioketones whose metrical parameters have been deposited with the Cambridge Structural Database. Classical hydrogen bonds of the N–H∙∙∙N and the N–H∙∙∙Br type are observed next to C–H∙∙∙S contacts. All synthesised compounds were characterised by microanalyses, single-crystal X-ray diffraction (except for [Nd(H2L1)2(NO3)3]), 1H NMR and IR spectroscopy.
- Full Text:
- Date Issued: 2016
- Authors: Madanhire, Tatenda
- Date: 2016
- Subjects: Rare earth metals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/13127 , vital:27154
- Description: The reactions of Ln(NO3)3∙6H2O (Ln = Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H2pydm) were investigated, and complexes with the formula, [Ln(H2pydm)2(NO3)2](NO3) (Ln = Pr or Nd) and [Er(H2pydm)3](NO3)3 were isolated. The ten-coordinate Pr(III) and Nd(III) compounds crystallise in the triclinic space group P-1 while the nine-coordinate Er(III) complex crystallises in the monoclinic system (P21/n). The reaction of PrCl3∙6H2O with H2pydm yielded the compound, [Pr(H2pydm)3](Cl)3, that crystallises in the monoclinic system, space group P21/c with α = 90, β = 98.680(1) and γ = 90°. The nine-coordinate Pr(III) ion is bound to three H2pydm ligands, with bond distances Pr-O 2.455(2)-2.478(2) Å and Pr-N 2.6355(19)-2.64(2) Å. X-ray crystal structures of all the H2pydm complexes reveal that the ligand coordinates tridentately, via the pyridyl nitrogen atom and the two hydroxyl oxygen atoms. The electronic absorption spectra of complexes show 4f-4f transitions. Rare-earth complexes, [Ln(H2L1)2(NO3)3] [Ln = Gd, Ho or Nd], were also prepared from a Schiff base. The X-ray single-crystal diffraction studies and SHAPE analyses of the Gd(III) and Ho(III) complexes shows that the complexes are ten-coordinate and exhibit distorted tetradecahedron geometries. With proton migration occurring from the phenol group to the imine function, complexation of the lanthanides to the ligand gives the ligand a zwitterionic phenoxo-iminium form. A phenolate oxygen-bridged dinuclear complex, [Ce2(H2L1)(ovan)3(NO3)3], has been obtained by reacting Ce(NO3)3∙6H2O with an o-vanillin derived Schiff base ligand, 2-((E)-(1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (H2L1). Hydrolysis of the Schiff base occurred to yield o-vanillin, which bridged two cerium atoms with the Ce∙∙∙Ce distance equal to 3.823 Å. The Ce(III) ions are both tencoordinate, but have different coordination environments, showing tetradecahedron and staggered dodecahedron geometries, respectively. The reaction of salicylaldehyde-N(4)-diethylthiosemicarbazone (H2L2) in the presence of hydrated Ln(III) nitrates led to the isolation of two novel compounds: (E)-2[(ortho-hydroxy)benzylidene]-2-(thiomethyl)-thionohydrazide (1) and bis[2,3-diaza4-(2-hydroxyphenyl)-1-thiomethyl-buta-1,3-diene]disulfide. The latter is a dimer of the former. For this asymmetric Schiff base, 1 and the symmetric disulfide, classical hydrogen bonds of the O–H∙∙∙N as well as N–H∙∙∙S (for 1) type are apparent next to C–H∙∙∙O contacts. 4-(4-Bromophenyl)-1-(propan-2-ylidene)thiosemicarbazide was also prepared upon reacting 4-(4-bromophenyl)-3-thiosemicarbazide with acetone in the presence of ethanol and La(NO3)3∙6H2O. The C=S bond length was found to be 1.6686(16) Å which is in good agreement with other thioketones whose metrical parameters have been deposited with the Cambridge Structural Database. Classical hydrogen bonds of the N–H∙∙∙N and the N–H∙∙∙Br type are observed next to C–H∙∙∙S contacts. All synthesised compounds were characterised by microanalyses, single-crystal X-ray diffraction (except for [Nd(H2L1)2(NO3)3]), 1H NMR and IR spectroscopy.
- Full Text:
- Date Issued: 2016
The development of the emerging technologies sustainability assessment (ETSA) and its application in the design of a bioprocess for the treatment of wine distillery effluent
- Authors: Khan, Nuraan
- Date: 2005
- Subjects: Technology assessment , Wine and wine making -- Waste disposal , Distilleries -- Waste disposal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3953 , http://hdl.handle.net/10962/d1004012 , Technology assessment , Wine and wine making -- Waste disposal , Distilleries -- Waste disposal
- Description: Emerging Technologies Sustainability Assessment (ETSA) is a new technology assessment tool that was developed in order to compare emerging processes or technologies to existing alternatives. It utilizes infoIDlation modules, with the minimum use of resources such as time and money, in order to deteIDline if the process under development is comparatively favourable and should be developed beyond the early conceptual phase. The preliminary ETSA is vital in order to identify the gaps in the existing information and the specific methodologies to be used for data capture and analysis. The use of experimental design tools, such as Design-Expert, can facilitate rapid and efficient collection of necessary data and fits in well with the rationale for the ETSA. Wine distillery effluent (vinasse) is the residue left after alcohol has been distilled from fennented grape juice. It is an acidic, darkly coloured effluent, with a high COD and polyphenol content. The most popular method of disposal of this effluent, land application, is no longer viable due to stricter legislation and pressure on the industry to better manage its wastes. Although the ability of whiterot fungi to degrade a number of pollutants is well-known, fungal treatment of wine distillery effluent is still in the conceptual phase. The perfoIDlance of the fungal remediation system was assessed experimentally in terms of COD removal and laccase production using Design-Expert. Although Pycnoporus sanguine us was found to be most efficient at COD removal (85%) from 30% vinasse, laccase production was low (0.021 U/I). The optimum design for economically viable fungal treatment used Trametespubescens. This fungus was able to remove over 50% of the COD from undiluted vinasse while producing almost 800U/l of the valuable laccase enzyme within three days. Since the effluent from the fungal system did not meet the legal limits for wastewater disposal, a two-stage aerobicanaerobic system is suggested to improve the quality of the effluent prior to disposal. The ETSA was used to assess the fungal technology in relation to the two current methods of vinasse treatment and disposal, namely land application and anaerobic digestion. Based on the ETSA, which considered environmental, social and economic impacts, the fungal system proved to be potentially competitive and further development of the technology is suggested.
- Full Text:
- Date Issued: 2005
- Authors: Khan, Nuraan
- Date: 2005
- Subjects: Technology assessment , Wine and wine making -- Waste disposal , Distilleries -- Waste disposal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3953 , http://hdl.handle.net/10962/d1004012 , Technology assessment , Wine and wine making -- Waste disposal , Distilleries -- Waste disposal
- Description: Emerging Technologies Sustainability Assessment (ETSA) is a new technology assessment tool that was developed in order to compare emerging processes or technologies to existing alternatives. It utilizes infoIDlation modules, with the minimum use of resources such as time and money, in order to deteIDline if the process under development is comparatively favourable and should be developed beyond the early conceptual phase. The preliminary ETSA is vital in order to identify the gaps in the existing information and the specific methodologies to be used for data capture and analysis. The use of experimental design tools, such as Design-Expert, can facilitate rapid and efficient collection of necessary data and fits in well with the rationale for the ETSA. Wine distillery effluent (vinasse) is the residue left after alcohol has been distilled from fennented grape juice. It is an acidic, darkly coloured effluent, with a high COD and polyphenol content. The most popular method of disposal of this effluent, land application, is no longer viable due to stricter legislation and pressure on the industry to better manage its wastes. Although the ability of whiterot fungi to degrade a number of pollutants is well-known, fungal treatment of wine distillery effluent is still in the conceptual phase. The perfoIDlance of the fungal remediation system was assessed experimentally in terms of COD removal and laccase production using Design-Expert. Although Pycnoporus sanguine us was found to be most efficient at COD removal (85%) from 30% vinasse, laccase production was low (0.021 U/I). The optimum design for economically viable fungal treatment used Trametespubescens. This fungus was able to remove over 50% of the COD from undiluted vinasse while producing almost 800U/l of the valuable laccase enzyme within three days. Since the effluent from the fungal system did not meet the legal limits for wastewater disposal, a two-stage aerobicanaerobic system is suggested to improve the quality of the effluent prior to disposal. The ETSA was used to assess the fungal technology in relation to the two current methods of vinasse treatment and disposal, namely land application and anaerobic digestion. Based on the ETSA, which considered environmental, social and economic impacts, the fungal system proved to be potentially competitive and further development of the technology is suggested.
- Full Text:
- Date Issued: 2005
Networking: enabling professional development and institutionalisation of environmental education courses in Southern Africa
- Authors: Lupele, Justin Kalaba
- Date: 2007
- Subjects: SADC Regional Environmental Education Programme Education -- Africa, Southern Environmental education -- Africa, Southern Environmental education -- Study and teaching -- Africa, Southern
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1678 , http://hdl.handle.net/10962/d1003561
- Description: This study was aimed at understanding how networking can enable or constrain professional development and institutionalisation of environmental education courses in southern Africa in the context of the Course Development Network (CDN), a project of the Southern Africa Development Community Regional Environmental Education Programme (SADC REEP). The study involved 12 institutions (each institution was represented in the CDN by a staff member) in eight SADC member states. It was contextualized through a review of social, political, environmental and educational developments in southern Africa, with specific reference to regionalization processes, as the SADC REEF is constituted under this post-colonial political framework. Relational philosophy informed the research process and methodology. The philosophy underpinned three distinct, yet related theoretical perspectives namely: critical realism, which provided the ontological perspectives of the study; Actor Network Theory; and Community of Practice, which provided the epistemological perspectives. Data was generated during a 33-month period in southern Africa and 12 months in the United Kingdom (and on a one week visit to Italy). During a 12 month Split Site Commonwealth Scholarship award, tenable at Manchester Metropolitan University in the United Kingdom, I studied the Environment and School Initiative (ENSI) and the Sustainability Education for European Primary Schools (SEEPS), to examine whether the same mechanisms that made them successful would apply to the CDN in the context of southern Africa. While these two case studies provided useful insight into the relationship between networking, professional development and institutionalization of environmental education programmes, they were not the main focus of the research. Data analysis was mainly through inductive, abductive and retroductive modes of inference. Inductive data analysis was done by means of Nvivo – a computer software package used for qualitative data analysis. The software aided in revealing features and relationships in the data in more depth as it allowed flexibility in working with data. Abduction is the interpretation of a phenomenon by means of a conceptual framework. In this study, I used Actor Network Theory (ANT) (Latour & Woolgar, 1979; Callon, 1986) and Community of Practice (COP) (Lave, 1988; Lave & Wenger, 1991; Fullan, 2003) as analytical conceptual frameworks to probe networking and professional development respectively. Data on institutionalisation of environmental education courses was analysed by means of retroductive mode of inference, which is a thought operation that enables the understanding of social reality beyond what is empirically observable or experienced. This study reveals that there were a number of necessary (internal) and contingent (external) factors that enabled or constrained networking, professional development and institutionalisation of environmental education courses in the context of the CDN. The key factors included existing cultural capital, donor political economy, power relations, poverty related factors and social transformation trends. The study found that relational approaches and the use of three relational theoretical lenses provided a broader lens which enabled this study to identify different dynamics, greater ontological depth and understanding of the relational dynamics and relations at play in the CDN beyond the participants' experience and observable events. The study also contends that networking can provide a support structure for social transformation and change in environmental education.
- Full Text:
- Date Issued: 2007
- Authors: Lupele, Justin Kalaba
- Date: 2007
- Subjects: SADC Regional Environmental Education Programme Education -- Africa, Southern Environmental education -- Africa, Southern Environmental education -- Study and teaching -- Africa, Southern
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1678 , http://hdl.handle.net/10962/d1003561
- Description: This study was aimed at understanding how networking can enable or constrain professional development and institutionalisation of environmental education courses in southern Africa in the context of the Course Development Network (CDN), a project of the Southern Africa Development Community Regional Environmental Education Programme (SADC REEP). The study involved 12 institutions (each institution was represented in the CDN by a staff member) in eight SADC member states. It was contextualized through a review of social, political, environmental and educational developments in southern Africa, with specific reference to regionalization processes, as the SADC REEF is constituted under this post-colonial political framework. Relational philosophy informed the research process and methodology. The philosophy underpinned three distinct, yet related theoretical perspectives namely: critical realism, which provided the ontological perspectives of the study; Actor Network Theory; and Community of Practice, which provided the epistemological perspectives. Data was generated during a 33-month period in southern Africa and 12 months in the United Kingdom (and on a one week visit to Italy). During a 12 month Split Site Commonwealth Scholarship award, tenable at Manchester Metropolitan University in the United Kingdom, I studied the Environment and School Initiative (ENSI) and the Sustainability Education for European Primary Schools (SEEPS), to examine whether the same mechanisms that made them successful would apply to the CDN in the context of southern Africa. While these two case studies provided useful insight into the relationship between networking, professional development and institutionalization of environmental education programmes, they were not the main focus of the research. Data analysis was mainly through inductive, abductive and retroductive modes of inference. Inductive data analysis was done by means of Nvivo – a computer software package used for qualitative data analysis. The software aided in revealing features and relationships in the data in more depth as it allowed flexibility in working with data. Abduction is the interpretation of a phenomenon by means of a conceptual framework. In this study, I used Actor Network Theory (ANT) (Latour & Woolgar, 1979; Callon, 1986) and Community of Practice (COP) (Lave, 1988; Lave & Wenger, 1991; Fullan, 2003) as analytical conceptual frameworks to probe networking and professional development respectively. Data on institutionalisation of environmental education courses was analysed by means of retroductive mode of inference, which is a thought operation that enables the understanding of social reality beyond what is empirically observable or experienced. This study reveals that there were a number of necessary (internal) and contingent (external) factors that enabled or constrained networking, professional development and institutionalisation of environmental education courses in the context of the CDN. The key factors included existing cultural capital, donor political economy, power relations, poverty related factors and social transformation trends. The study found that relational approaches and the use of three relational theoretical lenses provided a broader lens which enabled this study to identify different dynamics, greater ontological depth and understanding of the relational dynamics and relations at play in the CDN beyond the participants' experience and observable events. The study also contends that networking can provide a support structure for social transformation and change in environmental education.
- Full Text:
- Date Issued: 2007
Petrographic and geochemical characterisation of the hangingwall and the footwall rocks (the Dipeta and R.A.T. stratigraphic units) to the Kinsevere and Nambulwa copper ore deposits of the Lufilian Arc, southern Democratic Republic of Congo
- Authors: Nkulu, Robert Kankomba
- Date: 2020
- Subjects: Petrogenesis -- Congo (Democratic Republic) , Analytical geochemistry -- Congo (Democratic Republic) , Copper ores -- Congo (Democratic Republic) , Ore deposits -- Congo (Democratic Republic) , Katangan Sequence , Geological mapping -- Congo (Democratic Republic) , Central African Copperbelt (Congo and Zambia) , Lufilian Arc , Neoproterozoic Katangan R.A.T. (Roches Argilo Talqueuse) Subgroup , Dipeta Subgroup
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/142772 , vital:38115
- Description: The Kinsevere and Nambulwa copper deposits in the Democratic Republic of Congo (D.R.C.) are set in the eastern side of the Neoproterozoic Katanga Supergroup, forming the Lufilian Arc, resulting from a cratonic collision between the Congo and the Kalahari Cratons (ca.620-570_Ma). The Katanga Supergroup was deposited in an extensional rift setting with a sedimentary thickness succession ranging between 7 to 10 km, sub-divided into: − the Roan, the Nguba and the Kundelungu Groups. The stratigraphic column of the Roan Group consists of the R.A.T. (Roche Argilo Talqueuse), the Mines, the Dipeta and the Mwashya Subgroups. Three major deformation phases have been described characterised by complex multiphase tectonics related to a curved superposition of folded, thrust and sheared blocks. The rocks of the R.A.T., Mines and Dipeta Subgroups are recognised as blocks that occur within a stratiform to discordant and diapiritic megabreccia. The blocks were rafted upward with salt tectonics, resulting in the juxtaposition with the hangingwall and the footwall terranes. Therefore, in that context it has been found that the Dipeta may appear overlying the R.A.T. Subgroup through the unconformity decollement surface of heterogeneous breccia. The petrographic observations made of the R.A.T. and Dipeta samples indicates in both units the presence of detrital quartz and feldspar that have been altered and replaced by sericite and muscovite minerals. Gypsum is intimately associated with magnesite, showing an evaporitic environment domain, while magnesite is common as alteration phase both in the R.A.T. and Dipeta Subgroups. Pyrophyllite has been observed in the Dipeta, resulting from reaction of silica with the Kaolinite at low temperature. Accessory detrital minerals include zircon, as well as xenotime intergrown with altered Fe-Ti-oxide hematite, forming complex textures with disseminated Ti-oxides both in R.A.T. and Dipeta units. Major and trace element geochemistry indicates that the Dipeta is more dolomitic and magnesite while the R.A.T. is clay-rich. The Ti2O value of Dipeta and R.A.T samples is relatively low, ranging between 0.36 and 0.69 wt.% respectively, which suggest highly evolved felsic material in the protolith. This is consistent with interpretation based on the Al2O3/TiO2 ratio, which ranges between 18 and 23 for the R.A.T. and Dipeta respectively, indicating an intermediate to felsic granitoids as the protolith of R.A.T. and Dipeta siltstones. The Ti/Zr ratio of R.A.T. and Dipeta samples of less than 10, while, the higher La/Sc ratio of between 2.6 and 5.5 (for the R.A.T. and Dipeta respectively) indicate that both the R.A.T. and Dipeta are active continental and passive margin tectonic setting. Based on the geochemical variation with depth across the R.A.T. and Dipeta and their contact zone, a geochemical fingerprinting suggests that the ratio TiO2/Al2O3 appears to be useful and could be considered as a stratigraphic geochemical maker able to discriminate the R.A.T. and the Dipeta Subgroups during the geological mapping.
- Full Text:
- Date Issued: 2020
- Authors: Nkulu, Robert Kankomba
- Date: 2020
- Subjects: Petrogenesis -- Congo (Democratic Republic) , Analytical geochemistry -- Congo (Democratic Republic) , Copper ores -- Congo (Democratic Republic) , Ore deposits -- Congo (Democratic Republic) , Katangan Sequence , Geological mapping -- Congo (Democratic Republic) , Central African Copperbelt (Congo and Zambia) , Lufilian Arc , Neoproterozoic Katangan R.A.T. (Roches Argilo Talqueuse) Subgroup , Dipeta Subgroup
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/142772 , vital:38115
- Description: The Kinsevere and Nambulwa copper deposits in the Democratic Republic of Congo (D.R.C.) are set in the eastern side of the Neoproterozoic Katanga Supergroup, forming the Lufilian Arc, resulting from a cratonic collision between the Congo and the Kalahari Cratons (ca.620-570_Ma). The Katanga Supergroup was deposited in an extensional rift setting with a sedimentary thickness succession ranging between 7 to 10 km, sub-divided into: − the Roan, the Nguba and the Kundelungu Groups. The stratigraphic column of the Roan Group consists of the R.A.T. (Roche Argilo Talqueuse), the Mines, the Dipeta and the Mwashya Subgroups. Three major deformation phases have been described characterised by complex multiphase tectonics related to a curved superposition of folded, thrust and sheared blocks. The rocks of the R.A.T., Mines and Dipeta Subgroups are recognised as blocks that occur within a stratiform to discordant and diapiritic megabreccia. The blocks were rafted upward with salt tectonics, resulting in the juxtaposition with the hangingwall and the footwall terranes. Therefore, in that context it has been found that the Dipeta may appear overlying the R.A.T. Subgroup through the unconformity decollement surface of heterogeneous breccia. The petrographic observations made of the R.A.T. and Dipeta samples indicates in both units the presence of detrital quartz and feldspar that have been altered and replaced by sericite and muscovite minerals. Gypsum is intimately associated with magnesite, showing an evaporitic environment domain, while magnesite is common as alteration phase both in the R.A.T. and Dipeta Subgroups. Pyrophyllite has been observed in the Dipeta, resulting from reaction of silica with the Kaolinite at low temperature. Accessory detrital minerals include zircon, as well as xenotime intergrown with altered Fe-Ti-oxide hematite, forming complex textures with disseminated Ti-oxides both in R.A.T. and Dipeta units. Major and trace element geochemistry indicates that the Dipeta is more dolomitic and magnesite while the R.A.T. is clay-rich. The Ti2O value of Dipeta and R.A.T samples is relatively low, ranging between 0.36 and 0.69 wt.% respectively, which suggest highly evolved felsic material in the protolith. This is consistent with interpretation based on the Al2O3/TiO2 ratio, which ranges between 18 and 23 for the R.A.T. and Dipeta respectively, indicating an intermediate to felsic granitoids as the protolith of R.A.T. and Dipeta siltstones. The Ti/Zr ratio of R.A.T. and Dipeta samples of less than 10, while, the higher La/Sc ratio of between 2.6 and 5.5 (for the R.A.T. and Dipeta respectively) indicate that both the R.A.T. and Dipeta are active continental and passive margin tectonic setting. Based on the geochemical variation with depth across the R.A.T. and Dipeta and their contact zone, a geochemical fingerprinting suggests that the ratio TiO2/Al2O3 appears to be useful and could be considered as a stratigraphic geochemical maker able to discriminate the R.A.T. and the Dipeta Subgroups during the geological mapping.
- Full Text:
- Date Issued: 2020
Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands
- Yumata, Nonzaliseko Christine
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
Utilising value stream mapping to improve operations at Transwerk Uitenhage
- Authors: Silo, Andile Elliot
- Date: 2006
- Subjects: Production engineering , Production planning
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:8760 , http://hdl.handle.net/10948/604 , http://hdl.handle.net/10948/d1011684 , Production engineering , Production planning
- Description: Transwerk is a business uint of Transnet. It was established in 1940. Since 1940 unti 1994, Transwerk operated as the engineering section of Spoornet and was known as South African Railways. Transwerk emancipated in 1994 and had plants in all nine provinces of South Africa. In the past, trains were hauled by steam locomatives, which were manually operated. With the improvement of technology, steam locomotives were replaced by diesel locomotives. The recent technology improvement brought about electric locomotives which are more reliable than diesel locomotives.Trnaswerk has a plant in the Eastern Cape Province which is situated in Uitenhage. This plant focuses on refurbishing wagins for Spoornet. This research is about improving the refurbishing processes of Transwerk Uitenhage.
- Full Text:
- Date Issued: 2006
- Authors: Silo, Andile Elliot
- Date: 2006
- Subjects: Production engineering , Production planning
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:8760 , http://hdl.handle.net/10948/604 , http://hdl.handle.net/10948/d1011684 , Production engineering , Production planning
- Description: Transwerk is a business uint of Transnet. It was established in 1940. Since 1940 unti 1994, Transwerk operated as the engineering section of Spoornet and was known as South African Railways. Transwerk emancipated in 1994 and had plants in all nine provinces of South Africa. In the past, trains were hauled by steam locomatives, which were manually operated. With the improvement of technology, steam locomotives were replaced by diesel locomotives. The recent technology improvement brought about electric locomotives which are more reliable than diesel locomotives.Trnaswerk has a plant in the Eastern Cape Province which is situated in Uitenhage. This plant focuses on refurbishing wagins for Spoornet. This research is about improving the refurbishing processes of Transwerk Uitenhage.
- Full Text:
- Date Issued: 2006
Rhenium complexes with multidentate benzazoles and related N,X-donor (X = N, O, S) ligands
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
- Authors: Potgieter, Kim Carey
- Date: 2012
- Subjects: Rhenium , Benzimidazoles , Ligands (Biochemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10438 , http://hdl.handle.net/10948/d1020773
- Description: The coordination behaviour of 4-aminoantipyrine (H2pap) and its Schiff base derivatives with the oxorhenium(V) and tricarbonyl rhenium(I) cores are reported. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with H2pap were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The reactions of trans-[ReOBr3(PPh3)2] and cis-[ReO2I(PPh3)2] with -(2-aminobenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (H2nap) and 4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (Hoap) are also reported. The complexes cis-[Re(nap)Br2(PPh3)]Br, [ReO(OEt)(Hnap)(PPh3)]I and [ReO(OMe)(oap)(PPh3)]I were isolated and structurally characterized. The reactions of the Schiff base derivatives 1,2-(diimino-4’-antipyrinyl)ethane (dae) and 2,6-bis(4-amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one)pyridine (bap) with [Re(CO)5X] (X = Br or Cl) produced fac-[Re(CO)3(dae)Cl] and fac-[Re(CO)3(bap)Br] respectively. A series of rhenium(I) tricarbonyl complexes containing bidentate derivatives of aniline was synthesized and structurally characterized. With 1,2-diaminobenzene (Hpda) the ‘2+1’ complex salt fac-[Re(CO)3(κ1-Hpda)(κ2-Hpda)]Br was isolated, but with 2-mercaptophenol (Hspo) the bridged dimer [Re2(CO)7(spo)2] was found. The neutral complex [Re(CO)3(ons)(Hno)] was isolated from the reaction of [Re(CO)5Br] with 2-[(2-methylthio)benzylideneimino]phenol (Hons; Hno = 2-aminophenol), with ons coordinated as a bidentate chelate with a free SCH3 group. In the complex [Re(CO)3(Htpn)Br] (Htpn = N-(2-(methylthio)benzylidene)benzene-1,2-diamine) the potentially tridentate ligand Htpn is coordinated via the methylthiol sulfur and imino nitrogen atoms only, with a free amino group. These rhenium(I) complexes, with the exception of [Re2(CO)7(spo)2], revealed broad emissions centred around 535 nm. The reactions of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) compounds [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. The complexes adopt a trigonal prismatic geometry around the rhenium centre with average twists angles between 3.20-26.10˚. The E1/2 values for the Re(III)/Re(IV) redox couple were found to be 0.022, 0.142 and 0.126 V for [Re(Hatp)(ibsq)2].OPPh3, [Re(sbsq)3].OPPh3 and [Re(obsq)3].OPPh3 respectively. The reactions of the benzoxazole ligands, 3-(benzoxazol-2-yl)pyridin-2-ol (Hbop) and 5-amino-2-(benzoxazol-2-yl)phenol (Habo) with a [ReO]3+ precursor led to the rhenium(III) complex, [ReCl2(bop)(PPh3)2], and the complex salt, [ReO(abo)I(PPh3)2]ReO4, respectively. A variety of benzothiazole and benzimidazole derivatives were reacted with [Re(CO)5Br]. In the case of bis(benzothiazol-2-ylethyl)sulfide (bts), the neutral complex fac-[Re(CO)3(bts)Br] was obtained. The dimeric complexes (μ-dbt)2[Re(CO)3]2 and (μ-mbt)2[Re(CO)3]2 were formed when 1,3-bis(benzothiazol-2-yl)thiourea (Hdbt) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) were used as ligands. The reaction of 2,2’-(oxybis(methylene))bis(benzimidazole) (bmb) with [Re(CO)5Cl] resulted in the rhenium(I) complex salt fac-[Re(CO)3(bmb)]+, with the tri-μ-chlorohexacarbonyl dirhenate [Re2(CO)6Cl3]- as the counter anion. The neutral complex fac-[Re(CO)3(btp)Cl] was isolated from the reaction of the 2,9-bis(benzothiazol-2-yl)-1,10-phenanthroline (btp) ligand and [Re(CO)5Cl]. The reactions of trans-[ReOCl3(PPh3)2] with bis(benzimidazol-2-ylethyl)sulfide (btn) and 1-(benzothiazol-2-ylidene)-3-methylthiourea (Hmbt) led to the formation of the cationic compounds (μ-O)2[Re2O2(btn)2]I2 and [ReCl2(bte)(PPh3)2]Cl (bte = (benzothiazole-2-yl)-N-ethylidenemethanamine) respectively.
- Full Text:
- Date Issued: 2012
An investigation of parameter relationships in a high-speed digital multimedia environment
- Authors: Chigwamba, Nyasha
- Date: 2014
- Subjects: Multimedia communications , Digital communications , Local area networks (Computer networks) , Computer network architectures , Computer network protocols , Computer sound processing , Sound -- Recording and reproducing -- Digital techniques
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4725 , http://hdl.handle.net/10962/d1021153
- Description: With the rapid adoption of multimedia network technologies, a number of companies and standards bodies are introducing technologies that enhance user experience in networked multimedia environments. These technologies focus on device discovery, connection management, control, and monitoring. This study focused on control and monitoring. Multimedia networks make it possible for devices that are part of the same network to reside in different physical locations. These devices contain parameters that are used to control particular features, such as speaker volume, bass, amplifier gain, and video resolution. It is often necessary for changes in one parameter to affect other parameters, such as a synchronised change between volume and bass parameters, or collective control of multiple parameters. Thus, relationships are required between the parameters. In addition, some devices contain parameters, such as voltage, temperature, and audio level, that require constant monitoring to enable corrective action when thresholds are exceeded. Therefore, a mechanism for monitoring networked devices is required. This thesis proposes relationships that are essential for the proper functioning of a multimedia network and that should, therefore, be incorporated in standard form into a protocol, such that all devices can depend on them. Implementation mechanisms for these relationships were created. Parameter grouping and monitoring capabilities within mixing console implementations and existing control protocols were reviewed. A number of requirements for parameter grouping and monitoring were derived from this review. These requirements include a formal classification of relationship types, the ability to create relationships between parameters with different underlying value units, the ability to create relationships between parameters residing on different devices on a network, and the use of an event-driven mechanism for parameter monitoring. These requirements were the criteria used to govern the implementation mechanisms that were created as part of this study. Parameter grouping and monitoring mechanisms were implemented for the XFN protocol. The mechanisms implemented fulfil the requirements derived from the review of capabilities of mixing consoles and existing control protocols. The formal classification of relationship types was implemented within XFN parameters using lists that keep track of the relationships between each XFN parameter and other XFN parameters that reside on the same device or on other devices on the network. A common value unit, known as the global unit, was defined for use as the value format within value update messages between XFN parameters that have relationships. Mapping tables were used to translate the global unit values to application-specific (universal) units, such as decibels (dB). A mechanism for bulk parameter retrieval within the XFN protocol was augmented to produce an event-driven mechanism for parameter monitoring. These implementation mechanisms were applied to an XFN-protocol-compliant graphical control application to demonstrate their usage within an end user context. At the time of this study, the XFN protocol was undergoing standardisation within the Audio Engineering Society. The AES-64 standard has now been approved. Most of the implementation mechanisms resulting from this study have been incorporated into this standard.
- Full Text:
- Date Issued: 2014
- Authors: Chigwamba, Nyasha
- Date: 2014
- Subjects: Multimedia communications , Digital communications , Local area networks (Computer networks) , Computer network architectures , Computer network protocols , Computer sound processing , Sound -- Recording and reproducing -- Digital techniques
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4725 , http://hdl.handle.net/10962/d1021153
- Description: With the rapid adoption of multimedia network technologies, a number of companies and standards bodies are introducing technologies that enhance user experience in networked multimedia environments. These technologies focus on device discovery, connection management, control, and monitoring. This study focused on control and monitoring. Multimedia networks make it possible for devices that are part of the same network to reside in different physical locations. These devices contain parameters that are used to control particular features, such as speaker volume, bass, amplifier gain, and video resolution. It is often necessary for changes in one parameter to affect other parameters, such as a synchronised change between volume and bass parameters, or collective control of multiple parameters. Thus, relationships are required between the parameters. In addition, some devices contain parameters, such as voltage, temperature, and audio level, that require constant monitoring to enable corrective action when thresholds are exceeded. Therefore, a mechanism for monitoring networked devices is required. This thesis proposes relationships that are essential for the proper functioning of a multimedia network and that should, therefore, be incorporated in standard form into a protocol, such that all devices can depend on them. Implementation mechanisms for these relationships were created. Parameter grouping and monitoring capabilities within mixing console implementations and existing control protocols were reviewed. A number of requirements for parameter grouping and monitoring were derived from this review. These requirements include a formal classification of relationship types, the ability to create relationships between parameters with different underlying value units, the ability to create relationships between parameters residing on different devices on a network, and the use of an event-driven mechanism for parameter monitoring. These requirements were the criteria used to govern the implementation mechanisms that were created as part of this study. Parameter grouping and monitoring mechanisms were implemented for the XFN protocol. The mechanisms implemented fulfil the requirements derived from the review of capabilities of mixing consoles and existing control protocols. The formal classification of relationship types was implemented within XFN parameters using lists that keep track of the relationships between each XFN parameter and other XFN parameters that reside on the same device or on other devices on the network. A common value unit, known as the global unit, was defined for use as the value format within value update messages between XFN parameters that have relationships. Mapping tables were used to translate the global unit values to application-specific (universal) units, such as decibels (dB). A mechanism for bulk parameter retrieval within the XFN protocol was augmented to produce an event-driven mechanism for parameter monitoring. These implementation mechanisms were applied to an XFN-protocol-compliant graphical control application to demonstrate their usage within an end user context. At the time of this study, the XFN protocol was undergoing standardisation within the Audio Engineering Society. The AES-64 standard has now been approved. Most of the implementation mechanisms resulting from this study have been incorporated into this standard.
- Full Text:
- Date Issued: 2014
The coordination chemistry of Rhenium(V) with multidentate no-donor ligands
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009