Computerized Cataloguing: INF 323
- Chitsamatanga, N, Chikuni, P
- Authors: Chitsamatanga, N , Chikuni, P
- Date: 2009-11
- Language: English
- Type: Examination paper
- Identifier: vital:18084 , http://hdl.handle.net/10353/d1010764
- Description: Computerized Cataloguing: INF 323, degree examination November 2009.
- Full Text: false
- Date Issued: 2009-11
- Authors: Chitsamatanga, N , Chikuni, P
- Date: 2009-11
- Language: English
- Type: Examination paper
- Identifier: vital:18084 , http://hdl.handle.net/10353/d1010764
- Description: Computerized Cataloguing: INF 323, degree examination November 2009.
- Full Text: false
- Date Issued: 2009-11
Archives Administration: ARM 502
- Khayundi, F E, Chikuni, P, Ngulube, P
- Authors: Khayundi, F E , Chikuni, P , Ngulube, P
- Date: 2009-11
- Language: English
- Type: Examination paper
- Identifier: vital:18064 , http://hdl.handle.net/10353/d1010668
- Description: Archives Administration: ARM 502, Postgraduate diploma examination November 2009.
- Full Text: false
- Date Issued: 2009-11
- Authors: Khayundi, F E , Chikuni, P , Ngulube, P
- Date: 2009-11
- Language: English
- Type: Examination paper
- Identifier: vital:18064 , http://hdl.handle.net/10353/d1010668
- Description: Archives Administration: ARM 502, Postgraduate diploma examination November 2009.
- Full Text: false
- Date Issued: 2009-11
Introduction to Cataloguing & Classification: INF 122
- Authors: Chikuni, P R , Okemwa, O
- Date: 2010-01
- Subjects: Cataloging
- Language: English
- Type: Examination paper
- Identifier: vital:18000 , http://hdl.handle.net/10353/d1010574
- Description: Introduction to Cataloguing & Classification: INF 122, supplementary examination January 2010.
- Full Text: false
- Date Issued: 2010-01
- Authors: Chikuni, P R , Okemwa, O
- Date: 2010-01
- Subjects: Cataloging
- Language: English
- Type: Examination paper
- Identifier: vital:18000 , http://hdl.handle.net/10353/d1010574
- Description: Introduction to Cataloguing & Classification: INF 122, supplementary examination January 2010.
- Full Text: false
- Date Issued: 2010-01
Computerized Cataloguing: INF 323
- Authors: Chikuni, P R , Okemwa, O
- Date: 2010-01
- Subjects: Computerized Catalouging
- Language: English
- Type: Examination paper
- Identifier: vital:18003 , http://hdl.handle.net/10353/d1010577
- Description: Computerized Cataloguing: INF 323, Supplementary examination January 2010.
- Full Text: false
- Date Issued: 2010-01
- Authors: Chikuni, P R , Okemwa, O
- Date: 2010-01
- Subjects: Computerized Catalouging
- Language: English
- Type: Examination paper
- Identifier: vital:18003 , http://hdl.handle.net/10353/d1010577
- Description: Computerized Cataloguing: INF 323, Supplementary examination January 2010.
- Full Text: false
- Date Issued: 2010-01
Community radio and museum outreach: a case study of community radio practices to inform the environment and sustainability programmes of Livingstone Museum
- Authors: Muloongo, Arthanitius Henry
- Date: 2011
- Subjects: Community radio -- Zambia Livingstone Museum Museum outreach programs -- Zambia Environmental education -- Zambia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1454 , http://hdl.handle.net/10962/d1003335
- Description: This is a qualitative study whose purpose was to investigate the community radio education practices and the museum outreach education activities with a view to understanding how a museum-radio partnership may be used to engage the Livingstone community in environment and sustainability learning. Environment and sustainability issues require a community approach in order to bring about sustained responses to environmental challenges. As such, the study worked with social learning ideas of engaging the community in environment and sustainability learning. The data was generated mainly from face-to-face semi-structured interviews involving three community radio stations, Radio Listener Clubs and museum experts. The data generated was then presented to a strategy workshop involving the Livingstone Museum and Radio Musi-otunya staff. Arising from this workshop, recommendations were made about the possibility of the museum working in partnership with the radio to engage the community in environmental education. The study has shown that much of the museum environmental education activities have been confined to exhibitions and lectures within the museum building, which has affected the number of people being serviced by the museum. These education activities are arranged such that museum expert-led knowledge is presented to the audience with minimal community engagement on the environmental learning content. The study has also shown that community radio programming provides opportunities for community-led social learning which the Livingstone Museum could make use of to engage the community in environmental learning. Community radio programming allows community participation through Radio Listener Clubs, in identification and presentation of local environmental issues. This makes it a suitable tool to address locally relevant environmental issues, by the local community. Environmental issues are different from one place to another. Therefore environmental education approaches that bring issues into the museum may fail to address the different environmental education issues in different community context. The study concludes by recommending that Livingstone Museum should explore the use of community radio so that their expert knowledge and that of the radio producers could be used to shape environmental education programmes to go beyond awareness-raising.
- Full Text:
- Date Issued: 2011
- Authors: Muloongo, Arthanitius Henry
- Date: 2011
- Subjects: Community radio -- Zambia Livingstone Museum Museum outreach programs -- Zambia Environmental education -- Zambia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1454 , http://hdl.handle.net/10962/d1003335
- Description: This is a qualitative study whose purpose was to investigate the community radio education practices and the museum outreach education activities with a view to understanding how a museum-radio partnership may be used to engage the Livingstone community in environment and sustainability learning. Environment and sustainability issues require a community approach in order to bring about sustained responses to environmental challenges. As such, the study worked with social learning ideas of engaging the community in environment and sustainability learning. The data was generated mainly from face-to-face semi-structured interviews involving three community radio stations, Radio Listener Clubs and museum experts. The data generated was then presented to a strategy workshop involving the Livingstone Museum and Radio Musi-otunya staff. Arising from this workshop, recommendations were made about the possibility of the museum working in partnership with the radio to engage the community in environmental education. The study has shown that much of the museum environmental education activities have been confined to exhibitions and lectures within the museum building, which has affected the number of people being serviced by the museum. These education activities are arranged such that museum expert-led knowledge is presented to the audience with minimal community engagement on the environmental learning content. The study has also shown that community radio programming provides opportunities for community-led social learning which the Livingstone Museum could make use of to engage the community in environmental learning. Community radio programming allows community participation through Radio Listener Clubs, in identification and presentation of local environmental issues. This makes it a suitable tool to address locally relevant environmental issues, by the local community. Environmental issues are different from one place to another. Therefore environmental education approaches that bring issues into the museum may fail to address the different environmental education issues in different community context. The study concludes by recommending that Livingstone Museum should explore the use of community radio so that their expert knowledge and that of the radio producers could be used to shape environmental education programmes to go beyond awareness-raising.
- Full Text:
- Date Issued: 2011
Fish and fisheries of Bangweulu wetlands, Zambia
- Huchzermeyer, Carl Friedrich
- Authors: Huchzermeyer, Carl Friedrich
- Date: 2013
- Subjects: Bangweulu Swamps (Zambia) , Fisheries -- Zambia -- Bangweulu Swamps , Fishes -- Zambia -- Bangweulu Swamps , Fishery management -- Zambia -- Bangweulu Swamps , Fishing -- Zambia -- Bangweulu Swamps , Fishing -- Economic aspects -- Zambia -- Bangweulu Swamps , Fish stock assessment -- Zambia -- Bangweulu Swamps , Fish as food -- Zambia -- Bangweulu Swamps , Conservation of natural resources -- Zambia -- Bangweulu Swamps , Sustainable development -- Zambia -- Bangweulu Swamps
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5203 , http://hdl.handle.net/10962/d1003927 , Bangweulu Swamps (Zambia) , Fisheries -- Zambia -- Bangweulu Swamps , Fishes -- Zambia -- Bangweulu Swamps , Fishery management -- Zambia -- Bangweulu Swamps , Fishing -- Zambia -- Bangweulu Swamps , Fishing -- Economic aspects -- Zambia -- Bangweulu Swamps , Fish stock assessment -- Zambia -- Bangweulu Swamps , Fish as food -- Zambia -- Bangweulu Swamps , Conservation of natural resources -- Zambia -- Bangweulu Swamps , Sustainable development -- Zambia -- Bangweulu Swamps
- Description: Bangweulu Wetlands is a 6000 km² public-private-partnership conservation area in northeastern Zambia, lying on the south-eastern margins of the Bangweulu Swamps, Congo River system. The area is important for wildlife conservation, tourism and as a fishing ground for the local inhabitants. This study provides a baseline of the fish and fisheries of this area. The conservation area is situated on the transition zone between woodland, floodplain and swamp. A total of 42 fish species representing 12 taxonomic families were collected. The fish fauna of the area was characterised by a diversity of small cyprinids (14 species), cichlids (9 species), clariid catfishes (4 species) and mormyrids (4 species). Species such as Clarias gariepinus, C. ngamensis, Marcusenius macrolepidotus, Tilapia rendali, T. sparrmanii and several small Barbus species were shared with adjacent floodplain systems such as the upper Zambezi and Kafue rivers. Fishing was undertaken by fishing groups consisting of a fisherman and his family, or a group of men fishing together. Access to the fishing grounds was controlled by traditional fishing leaders, who collected tribute from fishermen. Fishing groups utilised fixed, distinct fishing areas determined by ancestry. The most important time for fishing was during the drawdown phase of the floodplains, from March until June. During the dry season fewer groups were engaged in fishing, with many having returned to farming activities. The main fishing methods of the floodplain fishery were basket traps and mosquito-mesh funnel nets set into earth fish barriers (fish weirs) constructed on the plains, various mesh sizes of gillnets, hook longlines and seine nets. The use of fish spears, drag baskets and piscicides was of lesser importance. Most fishing gears were constructed of a variety of natural and modern, manufactured materials. The fishery was multi-species and 23 fish species were recorded from in catch. The three most important species in the catches were C. gariepinus, T. rendalli and M. macrolepidotus. Together these contributed 67% by weight to the catch. Catch-per-unit-effort (CPUE) for the different gears was 0.4 ± 0.3 kg.trap.night⁻¹ for basket traps, 2.7 ± 4.6 kg.net.night⁻¹ for funnel nets, 0.3 ± 0.5 kg.50 m net.night⁻¹ for gill nets, 3.5 ± 6.3 kg.100 hooks.night⁻¹ for longlines, 1.79 ± 1.11 kg.haul⁻¹ for mosquito-mesh seine nets and 6.87 ± 6.27 kg.haul⁻¹ for larger-mesh seine nets. The weight of average daily landings of fishing groups, using a variety of gears was 7.8 ± 7.4 kg. Fishermen were able to maintain the same catch rate between dry and wet seasons, with no significant differences (p < 0.05) in daily landings between seasons. Yield per fisherman for a seven month season, which required 2-3 relocations due to falling water level, was 1.64 t based on catch assessment, and 1.9 t from a socio-economic survey. A tentative yield per area estimate for the area was 2I7 kg.ha⁻¹ over the three month shallow-floodplain fishing season. Most fish landed in the fishery were processed into sundried or smoke-dried products. These were used for 1) home consumption, 2) trade with village farmers (from up to 70 km inland of the fishing grounds) in exchange for staple starch meal, and 3) sold to urban fish traders, reaching markets as distant as Lubumbashi in Democratic Republic of Congo. Fish traders toured fishing camps to buy fish, supporting auxiliary industries such as transport and accommodation services. The price for dried fish at source was 3.14 ± 1.34 USDlkg and the market price reported for the Zambian Copperbelt was 6.14 ± 2.54 USD/kg. Typical returns on investment in fish trading were estimated as 68-77%. The fishery was considered to be biologically and socially sustainable. By harvesting a seasonally transient assemblage of species with high productivity and biological turnover rates and with life histories adapted to high mortality, fishermen were able to maintain a stable and viable livelihood. Management recommendations for the area were that a fisheries management plan be developed that would seek to strengthen the traditional system of rights-allocation, address problems between fishing and tourism activities, and enhance communication between fisheries and conservation stakeholders. To do this it was recommended that: 1) conservation authorities recognise the importance of the fishery, 2) no changes to current effort levels and fishing methods were necessary, 3) points 1 and 2 above be used to improve communication and trust between conservation authorities and fishermen, 4) customary resource-access mechanisms be understood and strengthened so that local inhabitants' rights to the resource are protected, 5) fishermen help formulate and accept conservation and tourism rules, 6) tourists and guides be made aware of the function of the fishery, 7) a fisheries management forum of key community, government and conservation stakeholders be formed to shape and implement the fisheries management plan, 8) locally-adapted bylaws be created to legitimise crucial floodplain gears currently considered illegal (e.g. mosquito-net gears, fish weirs), 9) no intervention to formalise fish trading be made, and 10) a trained person with a fisheries background be hired oversee the implementation of the recommendations.
- Full Text:
- Date Issued: 2013
- Authors: Huchzermeyer, Carl Friedrich
- Date: 2013
- Subjects: Bangweulu Swamps (Zambia) , Fisheries -- Zambia -- Bangweulu Swamps , Fishes -- Zambia -- Bangweulu Swamps , Fishery management -- Zambia -- Bangweulu Swamps , Fishing -- Zambia -- Bangweulu Swamps , Fishing -- Economic aspects -- Zambia -- Bangweulu Swamps , Fish stock assessment -- Zambia -- Bangweulu Swamps , Fish as food -- Zambia -- Bangweulu Swamps , Conservation of natural resources -- Zambia -- Bangweulu Swamps , Sustainable development -- Zambia -- Bangweulu Swamps
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5203 , http://hdl.handle.net/10962/d1003927 , Bangweulu Swamps (Zambia) , Fisheries -- Zambia -- Bangweulu Swamps , Fishes -- Zambia -- Bangweulu Swamps , Fishery management -- Zambia -- Bangweulu Swamps , Fishing -- Zambia -- Bangweulu Swamps , Fishing -- Economic aspects -- Zambia -- Bangweulu Swamps , Fish stock assessment -- Zambia -- Bangweulu Swamps , Fish as food -- Zambia -- Bangweulu Swamps , Conservation of natural resources -- Zambia -- Bangweulu Swamps , Sustainable development -- Zambia -- Bangweulu Swamps
- Description: Bangweulu Wetlands is a 6000 km² public-private-partnership conservation area in northeastern Zambia, lying on the south-eastern margins of the Bangweulu Swamps, Congo River system. The area is important for wildlife conservation, tourism and as a fishing ground for the local inhabitants. This study provides a baseline of the fish and fisheries of this area. The conservation area is situated on the transition zone between woodland, floodplain and swamp. A total of 42 fish species representing 12 taxonomic families were collected. The fish fauna of the area was characterised by a diversity of small cyprinids (14 species), cichlids (9 species), clariid catfishes (4 species) and mormyrids (4 species). Species such as Clarias gariepinus, C. ngamensis, Marcusenius macrolepidotus, Tilapia rendali, T. sparrmanii and several small Barbus species were shared with adjacent floodplain systems such as the upper Zambezi and Kafue rivers. Fishing was undertaken by fishing groups consisting of a fisherman and his family, or a group of men fishing together. Access to the fishing grounds was controlled by traditional fishing leaders, who collected tribute from fishermen. Fishing groups utilised fixed, distinct fishing areas determined by ancestry. The most important time for fishing was during the drawdown phase of the floodplains, from March until June. During the dry season fewer groups were engaged in fishing, with many having returned to farming activities. The main fishing methods of the floodplain fishery were basket traps and mosquito-mesh funnel nets set into earth fish barriers (fish weirs) constructed on the plains, various mesh sizes of gillnets, hook longlines and seine nets. The use of fish spears, drag baskets and piscicides was of lesser importance. Most fishing gears were constructed of a variety of natural and modern, manufactured materials. The fishery was multi-species and 23 fish species were recorded from in catch. The three most important species in the catches were C. gariepinus, T. rendalli and M. macrolepidotus. Together these contributed 67% by weight to the catch. Catch-per-unit-effort (CPUE) for the different gears was 0.4 ± 0.3 kg.trap.night⁻¹ for basket traps, 2.7 ± 4.6 kg.net.night⁻¹ for funnel nets, 0.3 ± 0.5 kg.50 m net.night⁻¹ for gill nets, 3.5 ± 6.3 kg.100 hooks.night⁻¹ for longlines, 1.79 ± 1.11 kg.haul⁻¹ for mosquito-mesh seine nets and 6.87 ± 6.27 kg.haul⁻¹ for larger-mesh seine nets. The weight of average daily landings of fishing groups, using a variety of gears was 7.8 ± 7.4 kg. Fishermen were able to maintain the same catch rate between dry and wet seasons, with no significant differences (p < 0.05) in daily landings between seasons. Yield per fisherman for a seven month season, which required 2-3 relocations due to falling water level, was 1.64 t based on catch assessment, and 1.9 t from a socio-economic survey. A tentative yield per area estimate for the area was 2I7 kg.ha⁻¹ over the three month shallow-floodplain fishing season. Most fish landed in the fishery were processed into sundried or smoke-dried products. These were used for 1) home consumption, 2) trade with village farmers (from up to 70 km inland of the fishing grounds) in exchange for staple starch meal, and 3) sold to urban fish traders, reaching markets as distant as Lubumbashi in Democratic Republic of Congo. Fish traders toured fishing camps to buy fish, supporting auxiliary industries such as transport and accommodation services. The price for dried fish at source was 3.14 ± 1.34 USDlkg and the market price reported for the Zambian Copperbelt was 6.14 ± 2.54 USD/kg. Typical returns on investment in fish trading were estimated as 68-77%. The fishery was considered to be biologically and socially sustainable. By harvesting a seasonally transient assemblage of species with high productivity and biological turnover rates and with life histories adapted to high mortality, fishermen were able to maintain a stable and viable livelihood. Management recommendations for the area were that a fisheries management plan be developed that would seek to strengthen the traditional system of rights-allocation, address problems between fishing and tourism activities, and enhance communication between fisheries and conservation stakeholders. To do this it was recommended that: 1) conservation authorities recognise the importance of the fishery, 2) no changes to current effort levels and fishing methods were necessary, 3) points 1 and 2 above be used to improve communication and trust between conservation authorities and fishermen, 4) customary resource-access mechanisms be understood and strengthened so that local inhabitants' rights to the resource are protected, 5) fishermen help formulate and accept conservation and tourism rules, 6) tourists and guides be made aware of the function of the fishery, 7) a fisheries management forum of key community, government and conservation stakeholders be formed to shape and implement the fisheries management plan, 8) locally-adapted bylaws be created to legitimise crucial floodplain gears currently considered illegal (e.g. mosquito-net gears, fish weirs), 9) no intervention to formalise fish trading be made, and 10) a trained person with a fisheries background be hired oversee the implementation of the recommendations.
- Full Text:
- Date Issued: 2013
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
Practical cataloguing: INF223
- Chitsamatanga, N, Chikuni, P
- Authors: Chitsamatanga, N , Chikuni, P
- Date: 2010-01
- Subjects: Cataloging
- Language: English
- Type: Examination paper
- Identifier: vital:18001 , http://hdl.handle.net/10353/d1010575
- Description: Practical cataloguing: INF223, Supplementary examination January 2010.
- Full Text: false
- Date Issued: 2010-01
- Authors: Chitsamatanga, N , Chikuni, P
- Date: 2010-01
- Subjects: Cataloging
- Language: English
- Type: Examination paper
- Identifier: vital:18001 , http://hdl.handle.net/10353/d1010575
- Description: Practical cataloguing: INF223, Supplementary examination January 2010.
- Full Text: false
- Date Issued: 2010-01
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
Contributions to the study of a class of optimal control problems on the matrix lie group SO(3)
- Authors: Rodgerson, Joanne Kelly
- Date: 2009 , 2013-07-12
- Subjects: Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5421 , http://hdl.handle.net/10962/d1007199 , Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Description: The purpose of this thesis is to investigate a class of four left-invariant optimal control problems on the special orthogonal group SO(3). The set of all control-affine left-invariant control systems on SO(3) can, without loss, be reduced to a class of four typical controllable left-invariant control systems on SO(3) . The left-invariant optimal control problem on SO(3) involves finding a trajectory-control pair on SO (3), which minimizes a cost functional, and satisfies the given dynamical constraints and boundary conditions in a fixed time. The problem is lifted to the cotangent bundle T*SO(3) = SO(3) x so (3)* using the optimal Hamiltonian on so(3)*, where the maximum principle yields the optimal control. In a contribution to the study of this class of optimal control problems on SO(3), the extremal equations on so(3)* (ident ified with JR3) are integrated via elliptic functions to obtain explicit expressions for the solution curves in each typical case. The energy-Casimir method is used to give sufficient conditions for non-linear stability of the equilibrium states. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2009
- Authors: Rodgerson, Joanne Kelly
- Date: 2009 , 2013-07-12
- Subjects: Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5421 , http://hdl.handle.net/10962/d1007199 , Matrix groups , Lie groups , Maximum principles (Mathematics) , Elliptic functions , Extremal problems (Mathematics)
- Description: The purpose of this thesis is to investigate a class of four left-invariant optimal control problems on the special orthogonal group SO(3). The set of all control-affine left-invariant control systems on SO(3) can, without loss, be reduced to a class of four typical controllable left-invariant control systems on SO(3) . The left-invariant optimal control problem on SO(3) involves finding a trajectory-control pair on SO (3), which minimizes a cost functional, and satisfies the given dynamical constraints and boundary conditions in a fixed time. The problem is lifted to the cotangent bundle T*SO(3) = SO(3) x so (3)* using the optimal Hamiltonian on so(3)*, where the maximum principle yields the optimal control. In a contribution to the study of this class of optimal control problems on SO(3), the extremal equations on so(3)* (ident ified with JR3) are integrated via elliptic functions to obtain explicit expressions for the solution curves in each typical case. The energy-Casimir method is used to give sufficient conditions for non-linear stability of the equilibrium states. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2009
Invariant optimal control on the three-dimensional semi-Euclidean group: control affine and quadratic Hamilton-Poisson systems
- Authors: Barrett, Dennis Ian
- Date: 2014
- Subjects: Automorphisms , Symmetry (Mathematics) , Lyapunov stability , Geometry, Riemannian , Geometry, Affine , Elliptic functions
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/64805 , vital:28605
- Description: In this thesis we consider invariant control systems and Hamilton-Poisson systems on the three dimensional semi-Euclidean group SE(1,1). We first classify the left-invariant control affine systems (under detached feedback equivalence). We provide a complete list of normal forms, as well as classifying conditions. As a corollary to this classification, we derive controllability criteria for control affine systems on SE(1,1). Secondly, we consider quadratic Hamilton-Poisson systems on the (minus) Lie-Poisson space se(1,1)*. These systems are classified up to an affine isomorphism. Six normal forms are identified for the homogeneous case, whereas sixteen representatives (including several infinite families) are obtained for the inhomogeneous systems. Thereafter we consider the stability and integration of the normal forms obtained. For all homogeneous systems, and a subclass of inhomogeneous systems, we perform a complete stability analysis and derive explicit expressions for all integral curves. (The extremal controls of a large class of optimal control problems on SE(1,1) are linearly related to these integral curves.) Lastly, we discuss the Riemannian and sub-Riemannian problems. The (left-invariant) Riemannian and sub-Riemannian structures on SE(1,1) are classified, up to isometric group automorphisms and scaling. Explicit expressions for the geodesics of the normalised structures are found.
- Full Text:
- Date Issued: 2014
- Authors: Barrett, Dennis Ian
- Date: 2014
- Subjects: Automorphisms , Symmetry (Mathematics) , Lyapunov stability , Geometry, Riemannian , Geometry, Affine , Elliptic functions
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/64805 , vital:28605
- Description: In this thesis we consider invariant control systems and Hamilton-Poisson systems on the three dimensional semi-Euclidean group SE(1,1). We first classify the left-invariant control affine systems (under detached feedback equivalence). We provide a complete list of normal forms, as well as classifying conditions. As a corollary to this classification, we derive controllability criteria for control affine systems on SE(1,1). Secondly, we consider quadratic Hamilton-Poisson systems on the (minus) Lie-Poisson space se(1,1)*. These systems are classified up to an affine isomorphism. Six normal forms are identified for the homogeneous case, whereas sixteen representatives (including several infinite families) are obtained for the inhomogeneous systems. Thereafter we consider the stability and integration of the normal forms obtained. For all homogeneous systems, and a subclass of inhomogeneous systems, we perform a complete stability analysis and derive explicit expressions for all integral curves. (The extremal controls of a large class of optimal control problems on SE(1,1) are linearly related to these integral curves.) Lastly, we discuss the Riemannian and sub-Riemannian problems. The (left-invariant) Riemannian and sub-Riemannian structures on SE(1,1) are classified, up to isometric group automorphisms and scaling. Explicit expressions for the geodesics of the normalised structures are found.
- Full Text:
- Date Issued: 2014
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
An investigation into strategies which enable South African women to break through the glass ceiling
- Authors: Peens, Maritha
- Date: 2003
- Subjects: Women executives -- South Africa , Women employees -- Promotions -- South Africa , Sex discrimination in employement -- South Africa , Sex discrimination against women -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:10898 , http://hdl.handle.net/10948/135 , Women executives -- South Africa , Women employees -- Promotions -- South Africa , Sex discrimination in employement -- South Africa , Sex discrimination against women -- South Africa
- Description: The objective of this study was to identify the strategies (personal and organisational) that would enable South African women to break through the glass ceiling. A questionaire was designed based on the strategies found in a literature study on the topic and used to gather inputs from executive women in South Africa. A combination of snowball and self-selection sampling was used. The questionaire was sent to 138 potential respondents, mostly by means of electronic mail. Of the 47 completed questionairs returned, 44 could be used. These were processed and anaylsed using Microsoft Excel spreadsheets and the STATISTICA Version 6 software. In generaL, support was found for personal strategies pertaining to career management, networking (especially the relationship building activities), the reconciliation of home and work responsibilities with the emphasis on building a support system, education, business and organisational insught, skills development and increased input, but not for the assimilation of masculine attributes. Networking opportunities and education, training and development activities were regarded as the organisational strategies with the strongest impact on career progress. The literature was confirmed regarding top management support, an organisational culture conducive to women's advancement, mentorship programmes and a few career development initiatives. Although more than half of the respondents had been exposed to employment equity and affirmative action programmes, they were perceived to have only little to moderate impact on career progress. This was also the case with diversity management programmes. Flexible work arrangements, career adaptation schemes and childcare facilities and programmes were seen as having had little impact on the respondents' career advancement. Only a few of the organisational practices to support women balancing family and work responsibilities were utilised by the respondents' employers. Respondents perceived personal strategies as having greater value than organisational strategies in their progress to executive levels.
- Full Text:
- Date Issued: 2003
An investigation into strategies which enable South African women to break through the glass ceiling
- Authors: Peens, Maritha
- Date: 2003
- Subjects: Women executives -- South Africa , Women employees -- Promotions -- South Africa , Sex discrimination in employement -- South Africa , Sex discrimination against women -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:10898 , http://hdl.handle.net/10948/135 , Women executives -- South Africa , Women employees -- Promotions -- South Africa , Sex discrimination in employement -- South Africa , Sex discrimination against women -- South Africa
- Description: The objective of this study was to identify the strategies (personal and organisational) that would enable South African women to break through the glass ceiling. A questionaire was designed based on the strategies found in a literature study on the topic and used to gather inputs from executive women in South Africa. A combination of snowball and self-selection sampling was used. The questionaire was sent to 138 potential respondents, mostly by means of electronic mail. Of the 47 completed questionairs returned, 44 could be used. These were processed and anaylsed using Microsoft Excel spreadsheets and the STATISTICA Version 6 software. In generaL, support was found for personal strategies pertaining to career management, networking (especially the relationship building activities), the reconciliation of home and work responsibilities with the emphasis on building a support system, education, business and organisational insught, skills development and increased input, but not for the assimilation of masculine attributes. Networking opportunities and education, training and development activities were regarded as the organisational strategies with the strongest impact on career progress. The literature was confirmed regarding top management support, an organisational culture conducive to women's advancement, mentorship programmes and a few career development initiatives. Although more than half of the respondents had been exposed to employment equity and affirmative action programmes, they were perceived to have only little to moderate impact on career progress. This was also the case with diversity management programmes. Flexible work arrangements, career adaptation schemes and childcare facilities and programmes were seen as having had little impact on the respondents' career advancement. Only a few of the organisational practices to support women balancing family and work responsibilities were utilised by the respondents' employers. Respondents perceived personal strategies as having greater value than organisational strategies in their progress to executive levels.
- Full Text:
- Date Issued: 2003
The classification of fuzzy groups of finite cyclic groups Zpn Zqm Zr and Zp1 Zp2 Zpn for distinct prime numbers p; q; r; p1; p2; ; pn and n;m 2 Z+
- Authors: Munywoki, Michael Mbindyo
- Date: 2018
- Subjects: Fuzzy sets Finite groups
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/17817 , vital:41295
- Description: Let G be the cyclic group Zpn _ Zqm _ Zr where p; q; r are distinct primes and n;m 2 Z+. Using the criss-cut method by Murali and Makamba, we determine in general the number of distinct fuzzy subgroups of G. This is achieved by using the maximal chains of subgroups of the respective groups, and the equivalence relation given in their research papers. For cases of m, the number of fuzzy subgroups is _rst given, from which the general pattern for G is achieved. Murali and Makamba discussed the number of fuzzy subgroups of Zpn _ Zqm using the cross-cut method. A brief revisit of the group Zpn _Zqm is done using the criss-cut method. The formulae for _nding the number of distinct fuzzy subgroups in each of the cases is given and proofs provided. Furthermore, we classify the fuzzy subgroups of the group Zp1_Zp2__ _ __Zpn for p1; p2; _ _ _ ; pn distinct primes and n 2 Z+ using the criss-cut method. An algorithm for counting the distinct fuzzy subgroups of this group is developed.
- Full Text:
- Date Issued: 2018
- Authors: Munywoki, Michael Mbindyo
- Date: 2018
- Subjects: Fuzzy sets Finite groups
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/17817 , vital:41295
- Description: Let G be the cyclic group Zpn _ Zqm _ Zr where p; q; r are distinct primes and n;m 2 Z+. Using the criss-cut method by Murali and Makamba, we determine in general the number of distinct fuzzy subgroups of G. This is achieved by using the maximal chains of subgroups of the respective groups, and the equivalence relation given in their research papers. For cases of m, the number of fuzzy subgroups is _rst given, from which the general pattern for G is achieved. Murali and Makamba discussed the number of fuzzy subgroups of Zpn _ Zqm using the cross-cut method. A brief revisit of the group Zpn _Zqm is done using the criss-cut method. The formulae for _nding the number of distinct fuzzy subgroups in each of the cases is given and proofs provided. Furthermore, we classify the fuzzy subgroups of the group Zp1_Zp2__ _ __Zpn for p1; p2; _ _ _ ; pn distinct primes and n 2 Z+ using the criss-cut method. An algorithm for counting the distinct fuzzy subgroups of this group is developed.
- Full Text:
- Date Issued: 2018
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
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
Tetra 4-(propargyloxy)phenoxy phthalocyanines: synthesis, spectroscopic, nonlinear optical and electrocatalytic properties
- Authors: Mwanza, Daniel
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics , Electrocatalysis , Spectrum analysis , Thermogravimetry , Phthalocyanines Spectra
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/65144 , vital:28695
- Description: This study presents the synthesis, spectroscopic, photophysical and theoretical characterisation of metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (MnTPrOPhOPc) tetra 4-(4-propargyloxy) phenoxy phthalocyanines. Thermal analysis using thermogravimetric analysis (TGA) confirmed the excellent thermal stability of synthesized tetra 4-(4- propargyloxy) phenoxy phthalocyanines. The metal complexes, CoTPrOPhOPc and MnTPrOPhOPc, exhibited better thermal stability when compared to H2TPrOPhOPc. The residual percentage weight remaining was approximately 70% for CoTPrOPhOPc and MnTPrOPhOPc and 45% for H2TPrOPhOPc after 600°C, clearly confirming the stability of the metal complexes. The MTPrOPhOPcs (where M = H2, Co and Mn) complexes exhibited excellent nonlinear optical properties with strong reverse saturable absorption (RSA), especially when 560 nm excitation laser was used. Their nonlinear optical properties followed this trend: H2TPrOPhOPc > CoTPrOPhOPc > MnTPrOPhOPc. According to the trend observed, the H2TPrOPhOPc was an excellent nonlinear optical limiter when compared to the CoTPrOPhOPc and MnTPrOPhOPc. All the investigated complexes exhibited optical limiting properties comparable to the phthalocyanine complexes reported in the literature. The MTPrOPhOPc complexes were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. For the electrocatalytic studies, the synthesized complexes were immobilized onto gold electrode surfaces pre-functionalized with phenylazide (Au-PAz) monolayer. Copper (I) catalyzed alkynyl-azide cycloaddition reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs modified gold surfaces (Au-PAz-MTPrOPhOPc) exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and surface characterisation of the functionalised gold electrode surfaces confirmed the presence of the MTPrOPhOPcs and their electroanalysis was excellent towards electrocatalytic reduction of H2O2, with the limit of detection (LoD) and limit of quantification (LoQ) in the ^M range. The electrocatalytic reduction peaks for H2O2 were observed at -0.37 V for Au-PAz-MnTPrOPhOPc and -0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-MnTPrOPhOPc and Au- PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution. , Thesis (MSc) -- Faculty of Science, Chemistry, 2017
- Full Text:
- Date Issued: 2017
- Authors: Mwanza, Daniel
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics , Electrocatalysis , Spectrum analysis , Thermogravimetry , Phthalocyanines Spectra
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/65144 , vital:28695
- Description: This study presents the synthesis, spectroscopic, photophysical and theoretical characterisation of metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (MnTPrOPhOPc) tetra 4-(4-propargyloxy) phenoxy phthalocyanines. Thermal analysis using thermogravimetric analysis (TGA) confirmed the excellent thermal stability of synthesized tetra 4-(4- propargyloxy) phenoxy phthalocyanines. The metal complexes, CoTPrOPhOPc and MnTPrOPhOPc, exhibited better thermal stability when compared to H2TPrOPhOPc. The residual percentage weight remaining was approximately 70% for CoTPrOPhOPc and MnTPrOPhOPc and 45% for H2TPrOPhOPc after 600°C, clearly confirming the stability of the metal complexes. The MTPrOPhOPcs (where M = H2, Co and Mn) complexes exhibited excellent nonlinear optical properties with strong reverse saturable absorption (RSA), especially when 560 nm excitation laser was used. Their nonlinear optical properties followed this trend: H2TPrOPhOPc > CoTPrOPhOPc > MnTPrOPhOPc. According to the trend observed, the H2TPrOPhOPc was an excellent nonlinear optical limiter when compared to the CoTPrOPhOPc and MnTPrOPhOPc. All the investigated complexes exhibited optical limiting properties comparable to the phthalocyanine complexes reported in the literature. The MTPrOPhOPc complexes were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. For the electrocatalytic studies, the synthesized complexes were immobilized onto gold electrode surfaces pre-functionalized with phenylazide (Au-PAz) monolayer. Copper (I) catalyzed alkynyl-azide cycloaddition reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs modified gold surfaces (Au-PAz-MTPrOPhOPc) exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and surface characterisation of the functionalised gold electrode surfaces confirmed the presence of the MTPrOPhOPcs and their electroanalysis was excellent towards electrocatalytic reduction of H2O2, with the limit of detection (LoD) and limit of quantification (LoQ) in the ^M range. The electrocatalytic reduction peaks for H2O2 were observed at -0.37 V for Au-PAz-MnTPrOPhOPc and -0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-MnTPrOPhOPc and Au- PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution. , Thesis (MSc) -- Faculty of Science, Chemistry, 2017
- Full Text:
- Date Issued: 2017
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
Contributions to the study of a class of optimal control problems on the orthogonal groups SO(3) and SO(4)
- Authors: Adams, Ross Montague
- Date: 2015
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64826 , vital:28608
- Description: In this thesis we investigate a class of invariant optimal control problems, and their associated quadratic Hamilton-Poisson systems, on the orthogonal groups SO(3) and SO(4). Specifically, we are concerned with the class of left-invariant control affine systems. We begin by classifying all cost-extended systems on SO(3) under cost equivalence. (Cost-extended systems are closely related to optimal control problems.) A classification of all quadratic Hamilton-Poisson systems on the (minus) Lie-Poisson space so(3)*, under affine equivalence, is also obtained. For the normal forms obtained in our classification (of Hamilton-Poisson systems) we investigate the (Lyapunov) stability nature of the equilibria using spectral and energy-Casimir methods. For a subclass of these systems, we obtain analytic expressions for the integral curves of the associated Hamiltonian vector fields in terms of (basic) Jacobi elliptic functions. The explicit relationship between the classification of cost-extended systems on SO(3) and the classification of quadratic Hamilton- Poisson systems on so(3)* is provided. On SO(4), a classification of all left-invariant control affine systems under L-equivalence is obtained. We then determine which of these representatives are controllable, thus obtaining a classification under detached feedback equivalence. We also obtain a partial classification of quadratic Hamilton-Poisson systems on the Lie-Poisson space so(4)*. An investigation of the stability nature of the equilibria for a subclass of these systems is also done. Several illustrative examples of optimal control problems on the orthogonal group SO(3) are provided. More specifically, we consider an optimal control problem corresponding to a representative of our classification (of cost-extended system) for each possible number of control inputs. For each of these problems, we obtain explicit expressions for the extremal trajectories on the homogeneous space S2 by projecting the extremal trajectories on the group SO(3). The examples provided show how our classifications of cost-extended systems and Hamilton-Poisson systems can be used to obtain the optimal controls and the extremal trajectories corresponding to a large class of optimal control problems on SO(3). An example of a four-input optimal control problem on SO(4) is also provided. This example is provided to show how the solutions of certain problems on SO(4) can be related to the solutions of certain optimal control problems on SO(3).
- Full Text:
- Date Issued: 2015
- Authors: Adams, Ross Montague
- Date: 2015
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64826 , vital:28608
- Description: In this thesis we investigate a class of invariant optimal control problems, and their associated quadratic Hamilton-Poisson systems, on the orthogonal groups SO(3) and SO(4). Specifically, we are concerned with the class of left-invariant control affine systems. We begin by classifying all cost-extended systems on SO(3) under cost equivalence. (Cost-extended systems are closely related to optimal control problems.) A classification of all quadratic Hamilton-Poisson systems on the (minus) Lie-Poisson space so(3)*, under affine equivalence, is also obtained. For the normal forms obtained in our classification (of Hamilton-Poisson systems) we investigate the (Lyapunov) stability nature of the equilibria using spectral and energy-Casimir methods. For a subclass of these systems, we obtain analytic expressions for the integral curves of the associated Hamiltonian vector fields in terms of (basic) Jacobi elliptic functions. The explicit relationship between the classification of cost-extended systems on SO(3) and the classification of quadratic Hamilton- Poisson systems on so(3)* is provided. On SO(4), a classification of all left-invariant control affine systems under L-equivalence is obtained. We then determine which of these representatives are controllable, thus obtaining a classification under detached feedback equivalence. We also obtain a partial classification of quadratic Hamilton-Poisson systems on the Lie-Poisson space so(4)*. An investigation of the stability nature of the equilibria for a subclass of these systems is also done. Several illustrative examples of optimal control problems on the orthogonal group SO(3) are provided. More specifically, we consider an optimal control problem corresponding to a representative of our classification (of cost-extended system) for each possible number of control inputs. For each of these problems, we obtain explicit expressions for the extremal trajectories on the homogeneous space S2 by projecting the extremal trajectories on the group SO(3). The examples provided show how our classifications of cost-extended systems and Hamilton-Poisson systems can be used to obtain the optimal controls and the extremal trajectories corresponding to a large class of optimal control problems on SO(3). An example of a four-input optimal control problem on SO(4) is also provided. This example is provided to show how the solutions of certain problems on SO(4) can be related to the solutions of certain optimal control problems on SO(3).
- Full Text:
- Date Issued: 2015
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