Invaded habitat incompatibility affects the suitability of the potential biological control agent Listronotus sordidus for Sagittaria platyphylla in South Africa
- Martin, Grant D, Coetzee, Julie A, Lloyd, Melissa, Nombewu, Sinoxolo E, Ndlovu, Mpilonhle S, Kwong, Raelene M
- Authors: Martin, Grant D , Coetzee, Julie A , Lloyd, Melissa , Nombewu, Sinoxolo E , Ndlovu, Mpilonhle S , Kwong, Raelene M
- Date: 2018
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/103926 , vital:32323 , https://doi.org/10.1080/09583157.2018.1460314
- Description: Sagittaria platyphylla (Engelmann) J.G. Smith (Alismataceae) was first recorded in South Africa in 2008 and is considered to be an emerging weed with naturalised populations occurring throughout the country. A biological control programme was initiated in Australia and surveys conducted between 2010 and 2012 yielded potential agents, including the crown feeding weevil, Listronotus sordidus Gyllenhal (Coleoptera: Curculionidae). The potential of L. sordidus as a candidate biological control agent against S. platyphylla in South Africa was examined. Although adult feeding was recorded on a number of plant species, oviposition and larval development indicated a narrow host range restricted to the Alismataceae. In South Africa, S. platyphylla populations are primarily found in inundated systems. However, laboratory studies showed that L. sordidus did not oviposit on inundated plants, potentially nullifying the impact of the insect on South African populations. It is suggested that even though L. sordidus is a damaging, specific agent, its limited impact on inundated plant populations in South Africa does not justify the inherent risk associated with the release of a biological control agent.
- Full Text: false
- Date Issued: 2018
- Authors: Martin, Grant D , Coetzee, Julie A , Lloyd, Melissa , Nombewu, Sinoxolo E , Ndlovu, Mpilonhle S , Kwong, Raelene M
- Date: 2018
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/103926 , vital:32323 , https://doi.org/10.1080/09583157.2018.1460314
- Description: Sagittaria platyphylla (Engelmann) J.G. Smith (Alismataceae) was first recorded in South Africa in 2008 and is considered to be an emerging weed with naturalised populations occurring throughout the country. A biological control programme was initiated in Australia and surveys conducted between 2010 and 2012 yielded potential agents, including the crown feeding weevil, Listronotus sordidus Gyllenhal (Coleoptera: Curculionidae). The potential of L. sordidus as a candidate biological control agent against S. platyphylla in South Africa was examined. Although adult feeding was recorded on a number of plant species, oviposition and larval development indicated a narrow host range restricted to the Alismataceae. In South Africa, S. platyphylla populations are primarily found in inundated systems. However, laboratory studies showed that L. sordidus did not oviposit on inundated plants, potentially nullifying the impact of the insect on South African populations. It is suggested that even though L. sordidus is a damaging, specific agent, its limited impact on inundated plant populations in South Africa does not justify the inherent risk associated with the release of a biological control agent.
- Full Text: false
- Date Issued: 2018
Could enemy release explain invasion success of Sagittaria platyphylla in Australia and South Africa?
- Kwong, Raelene M, Sagliocco, Jean L, Harms, Nathan E, Butler, Kym L, Martin, Grant D, Green, Peter T
- Authors: Kwong, Raelene M , Sagliocco, Jean L , Harms, Nathan E , Butler, Kym L , Martin, Grant D , Green, Peter T
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/419298 , vital:71632 , xlink:href="https://doi.org/10.1016/j.aquabot.2018.11.011"
- Description: Sagittaria platyphylla (delta arrowhead) is an emergent aquatic macrophyte native to southeastern United States of America that has been introduced into Australia and South Africa as an ornamental pond and aquarium plant. Compared to plants in the native range, S. platyphylla in the introduced range have greater reproductive capacity and form extensive infestations that dominate shallow waterbodies. One explanation for the invasive success of S. platyphylla in introduced countries is that plants are devoid of biotic pressures that would regulate population abundance in their native range (the enemy release hypothesis). We previously reported on field surveys that documented the number of pathogens and insect herbivores associated with S. platyphylla in native and introduced ranges. Here, we quantify the damage caused by these natural enemies to S. platyphylla in the two ranges. As predicted, damage to plants caused by pathogens and insect herbivores was much greater in the native than the introduced range at both the plant and population level. In introduced regions herbivory was low (less than 10%) in every plant part, while in North America insect damage to fruiting heads was 46% (of fruiting heads attacked), damage to leaves was between 33 to 57%, and internal herbivore damage to petioles and the inflorescence scapes was 56% and 43% respectively. Pathogen damage to leaves was between 39 to 57% of leaves per plant affected, compared to 9% in Australia and 8% in South Africa. This lack of biotic resistance from herbivores and disease may have facilitated S. platyphylla invasion in Australia and South Africa.
- Full Text:
- Date Issued: 2019
- Authors: Kwong, Raelene M , Sagliocco, Jean L , Harms, Nathan E , Butler, Kym L , Martin, Grant D , Green, Peter T
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/419298 , vital:71632 , xlink:href="https://doi.org/10.1016/j.aquabot.2018.11.011"
- Description: Sagittaria platyphylla (delta arrowhead) is an emergent aquatic macrophyte native to southeastern United States of America that has been introduced into Australia and South Africa as an ornamental pond and aquarium plant. Compared to plants in the native range, S. platyphylla in the introduced range have greater reproductive capacity and form extensive infestations that dominate shallow waterbodies. One explanation for the invasive success of S. platyphylla in introduced countries is that plants are devoid of biotic pressures that would regulate population abundance in their native range (the enemy release hypothesis). We previously reported on field surveys that documented the number of pathogens and insect herbivores associated with S. platyphylla in native and introduced ranges. Here, we quantify the damage caused by these natural enemies to S. platyphylla in the two ranges. As predicted, damage to plants caused by pathogens and insect herbivores was much greater in the native than the introduced range at both the plant and population level. In introduced regions herbivory was low (less than 10%) in every plant part, while in North America insect damage to fruiting heads was 46% (of fruiting heads attacked), damage to leaves was between 33 to 57%, and internal herbivore damage to petioles and the inflorescence scapes was 56% and 43% respectively. Pathogen damage to leaves was between 39 to 57% of leaves per plant affected, compared to 9% in Australia and 8% in South Africa. This lack of biotic resistance from herbivores and disease may have facilitated S. platyphylla invasion in Australia and South Africa.
- Full Text:
- Date Issued: 2019
Biogeographical comparison of the emergent macrophyte, Sagittaria platyphylla in its native and introduced ranges
- Kwong, Raelene M, Sagliocco, Jean L, Harms, Nathan E, Butler, Kym L, Green, Peter T, Martin, Grant D
- Authors: Kwong, Raelene M , Sagliocco, Jean L , Harms, Nathan E , Butler, Kym L , Green, Peter T , Martin, Grant D
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/419287 , vital:71631 , xlink:href="https://doi.org/10.1016/j.aquabot.2017.05.001"
- Description: Understanding why some plant species become invasive is important to predict and prevent future weed threats and identify appropriate management strategies. Many hypotheses have been proposed to explain why plants become invasive, yet few studies have quantitatively compared plant and population parameters between native and introduced range populations to gain an objective perspective on the causes of plant invasion. The present study uses a biogeographical field survey to compare morphological and reproductive traits and abundance between the native range (USA) and two introduced ranges (Australia and South Africa) of Sagittaria platyphylla (Engelm.) J.G. Sm (Alismataceae), a highly invasive freshwater macrophyte. Introduced and native populations differed in sexual reproductive output with the number of achenes per fruiting head and individual achene weight found to be 40% and 50% greater in introduced populations respectively. However, no other morphological traits were found to be consistently different between the native and both introduced ranges, especially after taking into account differences in environmental conditions between the three ranges. Although populations in introduced regions were larger and occupied greater percentage cover, no differences in plant density were evident. Our results suggest that, apart from sexual reproduction, many of the trait patterns observed in S. platyphylla are influenced by environmental and habitat conditions within the native and invaded ranges. We conclude that the enemy release hypothesis best explains the results observed for sexual reproduction. In particular, we hypothesise that a release from natural enemies, specifically a pre-dispersal seed predator, may induce reproductive plasticity in S. platyphylla.
- Full Text:
- Date Issued: 2017
- Authors: Kwong, Raelene M , Sagliocco, Jean L , Harms, Nathan E , Butler, Kym L , Green, Peter T , Martin, Grant D
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/419287 , vital:71631 , xlink:href="https://doi.org/10.1016/j.aquabot.2017.05.001"
- Description: Understanding why some plant species become invasive is important to predict and prevent future weed threats and identify appropriate management strategies. Many hypotheses have been proposed to explain why plants become invasive, yet few studies have quantitatively compared plant and population parameters between native and introduced range populations to gain an objective perspective on the causes of plant invasion. The present study uses a biogeographical field survey to compare morphological and reproductive traits and abundance between the native range (USA) and two introduced ranges (Australia and South Africa) of Sagittaria platyphylla (Engelm.) J.G. Sm (Alismataceae), a highly invasive freshwater macrophyte. Introduced and native populations differed in sexual reproductive output with the number of achenes per fruiting head and individual achene weight found to be 40% and 50% greater in introduced populations respectively. However, no other morphological traits were found to be consistently different between the native and both introduced ranges, especially after taking into account differences in environmental conditions between the three ranges. Although populations in introduced regions were larger and occupied greater percentage cover, no differences in plant density were evident. Our results suggest that, apart from sexual reproduction, many of the trait patterns observed in S. platyphylla are influenced by environmental and habitat conditions within the native and invaded ranges. We conclude that the enemy release hypothesis best explains the results observed for sexual reproduction. In particular, we hypothesise that a release from natural enemies, specifically a pre-dispersal seed predator, may induce reproductive plasticity in S. platyphylla.
- Full Text:
- Date Issued: 2017
Could enemy release explain invasion success of Sagittaria platyphylla in Australia and South Africa?.
- Kwong, Raelene M, Sagliocco, Jean Louis, Harms, Nathan E, Butler, Kym L, Martin, Grant D, Green, Peter T
- Authors: Kwong, Raelene M , Sagliocco, Jean Louis , Harms, Nathan E , Butler, Kym L , Martin, Grant D , Green, Peter T
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76881 , vital:30633 , https://doi.org/10.1016/j.aquabot.2018.11.011
- Description: Sagittaria platyphylla (delta arrowhead) is an emergent aquatic macrophyte native to southeastern United States of America that has been introduced into Australia and South Africa as an ornamental pond and aquarium plant. Compared to plants in the native range, S. platyphylla in the introduced range have greater reproductive capacity and form extensive infestations that dominate shallow waterbodies. One explanation for the invasive success of S. platyphylla in introduced countries is that plants are devoid of biotic pressures that would regulate population abundance in their native range (the enemy release hypothesis). We previously reported on field surveys that documented the number of pathogens and insect herbivores associated with S. platyphylla in native and introduced ranges. Here, we quantify the damage caused by these natural enemies to S. platyphylla in the two ranges. As predicted, damage to plants caused by pathogens and insect herbivores was much greater in the native than the introduced range at both the plant and population level. In introduced regions herbivory was low (less than 10%) in every plant part, while in North America insect damage to fruiting heads was 46% (of fruiting heads attacked), damage to leaves was between 33 to 57%, and internal herbivore damage to petioles and the inflorescence scapes was 56% and 43% respectively. Pathogen damage to leaves was between 39 to 57% of leaves per plant affected, compared to 9% in Australia and 8% in South Africa. This lack of biotic resistance from herbivores and disease may have facilitated S. platyphylla invasion in Australia and South Africa.
- Full Text:
- Date Issued: 2019
- Authors: Kwong, Raelene M , Sagliocco, Jean Louis , Harms, Nathan E , Butler, Kym L , Martin, Grant D , Green, Peter T
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76881 , vital:30633 , https://doi.org/10.1016/j.aquabot.2018.11.011
- Description: Sagittaria platyphylla (delta arrowhead) is an emergent aquatic macrophyte native to southeastern United States of America that has been introduced into Australia and South Africa as an ornamental pond and aquarium plant. Compared to plants in the native range, S. platyphylla in the introduced range have greater reproductive capacity and form extensive infestations that dominate shallow waterbodies. One explanation for the invasive success of S. platyphylla in introduced countries is that plants are devoid of biotic pressures that would regulate population abundance in their native range (the enemy release hypothesis). We previously reported on field surveys that documented the number of pathogens and insect herbivores associated with S. platyphylla in native and introduced ranges. Here, we quantify the damage caused by these natural enemies to S. platyphylla in the two ranges. As predicted, damage to plants caused by pathogens and insect herbivores was much greater in the native than the introduced range at both the plant and population level. In introduced regions herbivory was low (less than 10%) in every plant part, while in North America insect damage to fruiting heads was 46% (of fruiting heads attacked), damage to leaves was between 33 to 57%, and internal herbivore damage to petioles and the inflorescence scapes was 56% and 43% respectively. Pathogen damage to leaves was between 39 to 57% of leaves per plant affected, compared to 9% in Australia and 8% in South Africa. This lack of biotic resistance from herbivores and disease may have facilitated S. platyphylla invasion in Australia and South Africa.
- Full Text:
- Date Issued: 2019
Genetic analysis of native and introduced populations of the aquatic weed Sagittaria platyphylla – implications for biological control in Australia and South Africa
- Kwong, Raelene M, Broadhurst, Linda M, Keener, Brian R, Coetzee, Julie A, Knerr, Nunzio, Martin, Grant D
- Authors: Kwong, Raelene M , Broadhurst, Linda M , Keener, Brian R , Coetzee, Julie A , Knerr, Nunzio , Martin, Grant D
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76991 , vital:30653 , https://doi.org/10.1016/j.biocontrol.2017.06.002
- Description: Sagittaria platyphylla (Engelm.) J.G. Sm. (Alismataceae) is an emergent aquatic plant native to southern USA. Imported into Australia and South Africa as an ornamental and aquarium plant, the species is now a serious invader of shallow freshwater wetlands, slow-flowing rivers, irrigation channels, drains and along the margins of lakes and reservoirs. As a first step towards initiating a classical biological control program, a population genetic study was conducted to determine the prospects of finding compatible biological control agents and to refine the search for natural enemies to source populations with closest genetic match to Australian and South African genotypes. Using AFLP markers we surveyed genetic diversity and population genetic structure in 26 populations from the USA, 19 from Australia and 7 from South Africa. Interestingly, we have established that populations introduced into South Africa and to a lesser extent Australia have maintained substantial molecular genetic diversity comparable with that in the native range. Results from principal coordinates analysis, population graph theory and Bayesian-based clustering analysis all support the notion that introduced populations in Australia and South Africa were founded by multiple sources from the USA. Furthermore, the divergence of some Australian populations from the USA suggests that intraspecific hybridization between genetically distinct lineages from the native range may have occurred. The implications of these findings in relation to biological control are discussed.
- Full Text:
- Date Issued: 2017
- Authors: Kwong, Raelene M , Broadhurst, Linda M , Keener, Brian R , Coetzee, Julie A , Knerr, Nunzio , Martin, Grant D
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76991 , vital:30653 , https://doi.org/10.1016/j.biocontrol.2017.06.002
- Description: Sagittaria platyphylla (Engelm.) J.G. Sm. (Alismataceae) is an emergent aquatic plant native to southern USA. Imported into Australia and South Africa as an ornamental and aquarium plant, the species is now a serious invader of shallow freshwater wetlands, slow-flowing rivers, irrigation channels, drains and along the margins of lakes and reservoirs. As a first step towards initiating a classical biological control program, a population genetic study was conducted to determine the prospects of finding compatible biological control agents and to refine the search for natural enemies to source populations with closest genetic match to Australian and South African genotypes. Using AFLP markers we surveyed genetic diversity and population genetic structure in 26 populations from the USA, 19 from Australia and 7 from South Africa. Interestingly, we have established that populations introduced into South Africa and to a lesser extent Australia have maintained substantial molecular genetic diversity comparable with that in the native range. Results from principal coordinates analysis, population graph theory and Bayesian-based clustering analysis all support the notion that introduced populations in Australia and South Africa were founded by multiple sources from the USA. Furthermore, the divergence of some Australian populations from the USA suggests that intraspecific hybridization between genetically distinct lineages from the native range may have occurred. The implications of these findings in relation to biological control are discussed.
- Full Text:
- Date Issued: 2017
Biogeographical comparison of the emergent macrophyte, Sagittaria platyphylla in its native and introduced ranges
- Kwong, Raelene M, Sagliocco, Jean Louis, Harms, Nathan E, Butler, Kym L, Green, Peter T, Martin, Grant D
- Authors: Kwong, Raelene M , Sagliocco, Jean Louis , Harms, Nathan E , Butler, Kym L , Green, Peter T , Martin, Grant D
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76980 , vital:30652 , https://doi.org/10.1016/j.aquabot.2017.05.001
- Description: Understanding why some plant species become invasive is important to predict and prevent future weed threats and identify appropriate management strategies. Many hypotheses have been proposed to explain why plants become invasive, yet few studies have quantitatively compared plant and population parameters between native and introduced range populations to gain an objective perspective on the causes of plant invasion. The present study uses a biogeographical field survey to compare morphological and reproductive traits and abundance between the native range (USA) and two introduced ranges (Australia and South Africa) of Sagittaria platyphylla (Engelm.) J.G. Sm (Alismataceae), a highly invasive freshwater macrophyte. Introduced and native populations differed in sexual reproductive output with the number of achenes per fruiting head and individual achene weight found to be 40% and 50% greater in introduced populations respectively. However, no other morphological traits were found to be consistently different between the native and both introduced ranges, especially after taking into account differences in environmental conditions between the three ranges. Although populations in introduced regions were larger and occupied greater percentage cover, no differences in plant density were evident. Our results suggest that, apart from sexual reproduction, many of the trait patterns observed in S. platyphylla are influenced by environmental and habitat conditions within the native and invaded ranges. We conclude that the enemy release hypothesis best explains the results observed for sexual reproduction. In particular, we hypothesise that a release from natural enemies, specifically a pre-dispersal seed predator, may induce reproductive plasticity in S. platyphylla.
- Full Text:
- Date Issued: 2017
- Authors: Kwong, Raelene M , Sagliocco, Jean Louis , Harms, Nathan E , Butler, Kym L , Green, Peter T , Martin, Grant D
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76980 , vital:30652 , https://doi.org/10.1016/j.aquabot.2017.05.001
- Description: Understanding why some plant species become invasive is important to predict and prevent future weed threats and identify appropriate management strategies. Many hypotheses have been proposed to explain why plants become invasive, yet few studies have quantitatively compared plant and population parameters between native and introduced range populations to gain an objective perspective on the causes of plant invasion. The present study uses a biogeographical field survey to compare morphological and reproductive traits and abundance between the native range (USA) and two introduced ranges (Australia and South Africa) of Sagittaria platyphylla (Engelm.) J.G. Sm (Alismataceae), a highly invasive freshwater macrophyte. Introduced and native populations differed in sexual reproductive output with the number of achenes per fruiting head and individual achene weight found to be 40% and 50% greater in introduced populations respectively. However, no other morphological traits were found to be consistently different between the native and both introduced ranges, especially after taking into account differences in environmental conditions between the three ranges. Although populations in introduced regions were larger and occupied greater percentage cover, no differences in plant density were evident. Our results suggest that, apart from sexual reproduction, many of the trait patterns observed in S. platyphylla are influenced by environmental and habitat conditions within the native and invaded ranges. We conclude that the enemy release hypothesis best explains the results observed for sexual reproduction. In particular, we hypothesise that a release from natural enemies, specifically a pre-dispersal seed predator, may induce reproductive plasticity in S. platyphylla.
- Full Text:
- Date Issued: 2017
Predicting non-target impacts:
- Paynter, Quentin, Paterson, Iain D, Kwong, Raelene M
- Authors: Paynter, Quentin , Paterson, Iain D , Kwong, Raelene M
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/149982 , vital:38921 , https://doi.org/10.1016/j.cois.2020.02.002
- Description: Biocontrol of invasive alien weeds has produced great benefits, but concerns over undesirable impacts on non-target plants and/or indirect interactions between biocontrol agents and other biota impede the implementation of biocontrol in some countries. Although great strides have been made, continuing uncertainties predicting the realized host range of candidate agents is probably resulting in some being erroneously rejected due to overestimation of risk. Further refinement of host-range testing protocols is therefore desirable. Indirect interactions are inherently harder to predict, and the risk of both direct and indirect non-target impacts may change over time due to biocontrol agents evolving or expanding their range under climate change. Future research directions to better understand the risk of non-target impacts over time are discussed.
- Full Text:
- Date Issued: 2020
- Authors: Paynter, Quentin , Paterson, Iain D , Kwong, Raelene M
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/149982 , vital:38921 , https://doi.org/10.1016/j.cois.2020.02.002
- Description: Biocontrol of invasive alien weeds has produced great benefits, but concerns over undesirable impacts on non-target plants and/or indirect interactions between biocontrol agents and other biota impede the implementation of biocontrol in some countries. Although great strides have been made, continuing uncertainties predicting the realized host range of candidate agents is probably resulting in some being erroneously rejected due to overestimation of risk. Further refinement of host-range testing protocols is therefore desirable. Indirect interactions are inherently harder to predict, and the risk of both direct and indirect non-target impacts may change over time due to biocontrol agents evolving or expanding their range under climate change. Future research directions to better understand the risk of non-target impacts over time are discussed.
- Full Text:
- Date Issued: 2020
Managing the invasive aquatic plant Sagittaria platyphylla (Engelm.) J.G. Sm(Alismataceae): problems and prospects
- Ndlovu, Mpilonhle Sinothando
- Authors: Ndlovu, Mpilonhle Sinothando
- Date: 2020
- Subjects: Aquatic weeds -- Biological control -- South Africa , Sagittaria latifolia -- Biological control -- South Africa , Noxious weeds -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa , Listronotus , Insects as biological pest control agents
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167121 , vital:41439
- Description: Sagittaria platyphylla (Engelm.) J.G.Sm. (Alismataceae), commonly known as Delta arrowhead, is an invasive aquatic macrophyte native to southern United States of America (USA) that has become a serious weed in freshwater systems in South Africa, New Zealand, Australia, and recently China. In South Africa, the plant was first detected in Krantzkloof Nature Reserve, KwaZulu-Natal Province in 2008, and due to its known impact in other countries, it was listed as a Category 1a invader species under the National Environmental Management: Biodiversity Act 2004 (NEM: BA). This listing required mechanical and chemical control methods to be implemented by the South African National Biodiversity Institute’s (SANBI), Invasive Species Programme (ISP), with the aim of eradicating the weed. Despite the eradication efforts, by 2016, the weed was recognized as one of the country’s top 10 worst and fastest spreading invasive alien plants. Since its introduction in 2008, the plant has spread both within and between sites in South Africa, increasing from one site in 2008 to 72 sites by 2019. Once introduced into lotic systems, the plant spread rapidly downstream, in some cases up to 120km within six years, with an average of 10 km per year. Extirpation over the last ten years was only possible at a limited number of sites. Under the current management approach, the invasion is foreseen to spread to new sites within a 5 km radius of the current populations. Due to the failure of conventional control mechanisms, biological control is currently being considered as a potential control option. Four potential biological control agents are under investigation, but none have been released. Amongst them is the fruit and flower feeding weevil Listronotus appendiculatus Bohm. (Coleoptera: Curculionidae) which showed most potential as a suitable biological control agent. This study demonstrated that L. appendiculatus herbivory negatively influenced the overall fitness of S. platyphylla by reducing the plant’s growth rate and above ground biomass. Listronotus appendiculatus herbivory also reduced the plant’s size and the potential to kill adult plants. Most importantly, L. appendiculatus larval feeding damage significantly reduce viable-germinating seeds, the weed’s primary dispersal mechanism. Therefore, a biological control programme is advised to be integrated within the current management plan.
- Full Text:
- Date Issued: 2020
- Authors: Ndlovu, Mpilonhle Sinothando
- Date: 2020
- Subjects: Aquatic weeds -- Biological control -- South Africa , Sagittaria latifolia -- Biological control -- South Africa , Noxious weeds -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa , Listronotus , Insects as biological pest control agents
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167121 , vital:41439
- Description: Sagittaria platyphylla (Engelm.) J.G.Sm. (Alismataceae), commonly known as Delta arrowhead, is an invasive aquatic macrophyte native to southern United States of America (USA) that has become a serious weed in freshwater systems in South Africa, New Zealand, Australia, and recently China. In South Africa, the plant was first detected in Krantzkloof Nature Reserve, KwaZulu-Natal Province in 2008, and due to its known impact in other countries, it was listed as a Category 1a invader species under the National Environmental Management: Biodiversity Act 2004 (NEM: BA). This listing required mechanical and chemical control methods to be implemented by the South African National Biodiversity Institute’s (SANBI), Invasive Species Programme (ISP), with the aim of eradicating the weed. Despite the eradication efforts, by 2016, the weed was recognized as one of the country’s top 10 worst and fastest spreading invasive alien plants. Since its introduction in 2008, the plant has spread both within and between sites in South Africa, increasing from one site in 2008 to 72 sites by 2019. Once introduced into lotic systems, the plant spread rapidly downstream, in some cases up to 120km within six years, with an average of 10 km per year. Extirpation over the last ten years was only possible at a limited number of sites. Under the current management approach, the invasion is foreseen to spread to new sites within a 5 km radius of the current populations. Due to the failure of conventional control mechanisms, biological control is currently being considered as a potential control option. Four potential biological control agents are under investigation, but none have been released. Amongst them is the fruit and flower feeding weevil Listronotus appendiculatus Bohm. (Coleoptera: Curculionidae) which showed most potential as a suitable biological control agent. This study demonstrated that L. appendiculatus herbivory negatively influenced the overall fitness of S. platyphylla by reducing the plant’s growth rate and above ground biomass. Listronotus appendiculatus herbivory also reduced the plant’s size and the potential to kill adult plants. Most importantly, L. appendiculatus larval feeding damage significantly reduce viable-germinating seeds, the weed’s primary dispersal mechanism. Therefore, a biological control programme is advised to be integrated within the current management plan.
- Full Text:
- Date Issued: 2020
An account and explanation of the increased role played by women in the modern Olympic games 1896-1972
- Authors: Handley, Bridget Mary
- Date: 1976
- Subjects: Olympics -- History , Sports for women -- History , Women Olympic athletes
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5150 , http://hdl.handle.net/10962/d1012149 , Olympics -- History , Sports for women -- History , Women Olympic athletes
- Description: This thesis is concerned with the participation of women and girls in the Olympic Games. In these days of women's liberation it seemed appropriate to try to put together the knowledge available about women competitors and their participation in the Olympics. I have tried to set out an overall view with some historical background and then an account leading up to the initial and continuing participation of women in the Games and showing the reasons for the slow beginning and the gradual increase in numbers of competitors and sports. I have also tried to evaluate some well known myths and misconceptions concerning participation and made an attempt with the use of research data to disprove many of these.
- Full Text:
- Date Issued: 1976
- Authors: Handley, Bridget Mary
- Date: 1976
- Subjects: Olympics -- History , Sports for women -- History , Women Olympic athletes
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5150 , http://hdl.handle.net/10962/d1012149 , Olympics -- History , Sports for women -- History , Women Olympic athletes
- Description: This thesis is concerned with the participation of women and girls in the Olympic Games. In these days of women's liberation it seemed appropriate to try to put together the knowledge available about women competitors and their participation in the Olympics. I have tried to set out an overall view with some historical background and then an account leading up to the initial and continuing participation of women in the Games and showing the reasons for the slow beginning and the gradual increase in numbers of competitors and sports. I have also tried to evaluate some well known myths and misconceptions concerning participation and made an attempt with the use of research data to disprove many of these.
- Full Text:
- Date Issued: 1976
The tuber-feeding weevil Listronotus frontalis as a candidate biological control agent for the invasive semi-aquatic plant Sagittaria platyphylla within South Africa
- Authors: Rogers, Daniel James
- Date: 2021-10
- Subjects: Listronotus South Africa , Arrowhead (Plants) South Africa , Arrowhead (Plants) Biological control South Africa , Invasive plants Biological control South Africa , Insects as biological pest control agents South Africa , Plant populations South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/190731 , vital:45023
- Description: Sagittaria platyphylla (Engelm.) J.G.Sm. (Alismataceae) is an invasive, aquatic macrophyte originating in the southern United States of America. In South Africa, the plant was first detected in Krantzkloof Nature Reserve, KwaZulu-Natal Province in 2008, and due to its known impact in other countries, it was listed as a Category 1a invader species under the National Environmental Management: Biodiversity Act 2004 (NEM:BA). This invasive plant has proved difficult to manage due to its varied growth forms and reproductive strategies, such as prolific seed and below ground tuber production. Due to the limitations of conventional control mechanisms, biological control is currently being considered as a potential control option. The tuber feeding weevil Listronotus frontalis LeConte (Coleoptera: Curculionidae) has been identified as a candidate biological control agent for this invasive species. The aims of this study were twofold; to firstly determine the importance of tubers to S. platyphylla populations growing in South Africa; and secondly, to determine the biology and suitability of L. frontalis, a tuber feeder, as a candidate biological control agent. Surveys of S. platyphylla populations in South Africa showed that tubers were found in all sampled sites, except for Krantzkloof Nature reserve in KwaZulu-Natal Province. The highest number of tubers was 97.75 ± 10.62 (SE) m-2 recorded at Jonkershoek in the Western Cape Province. Monthly sampling from two sites in the Eastern Cape Province, the Makana Botanical Gardens and Maden Dam showed that neither season nor water depth affected tuber production. However, the mean number of tubers as well as mass of tubers sampled, were consistently higher (F(1,179) = 20.9542, P < 0.0001) and heavier (F(1, 857) = 585.7293, P < 0.0001) at the Botanical Gardens than at Maden Dam, respectively. The study showed that tubers are an important life stage of S. platyphylla populations and may vary in size and abundance between and within sites. The tuber feeding weevil was shown to develop from egg to ovipositing adult within just over 40 days. Females were recorded to lay up to 48 eggs within a period of one week. Impact studies showed that adult feeding led to a reduction in all but one of the 11 measured plant growth and developmental measurements, including a reduction in the mean mass of the above-ground plant material (F(2,2743) = 12.05, P = 0.002) as well as a reduction in size and abundance of tubers (F(2,58.47) = 9.756, P = 0.0006) and stolons(F(14.943) = 8.7577, P = 0.003). These results are encouraging and suggest that if the insect is released in South Africa, it may prove to be a valuable biocontrol agent. It is concluded that, until suitable biological control options become available in South Africa, the chemical and mechanical control measures currently implemented should continue, however, controlling tubers should be considered during the planning and implementation of these strategies. , Thesis (MSc) -- Faculty of Science, Zoology and Entomology, 2021
- Full Text:
- Date Issued: 2021-10
- Authors: Rogers, Daniel James
- Date: 2021-10
- Subjects: Listronotus South Africa , Arrowhead (Plants) South Africa , Arrowhead (Plants) Biological control South Africa , Invasive plants Biological control South Africa , Insects as biological pest control agents South Africa , Plant populations South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/190731 , vital:45023
- Description: Sagittaria platyphylla (Engelm.) J.G.Sm. (Alismataceae) is an invasive, aquatic macrophyte originating in the southern United States of America. In South Africa, the plant was first detected in Krantzkloof Nature Reserve, KwaZulu-Natal Province in 2008, and due to its known impact in other countries, it was listed as a Category 1a invader species under the National Environmental Management: Biodiversity Act 2004 (NEM:BA). This invasive plant has proved difficult to manage due to its varied growth forms and reproductive strategies, such as prolific seed and below ground tuber production. Due to the limitations of conventional control mechanisms, biological control is currently being considered as a potential control option. The tuber feeding weevil Listronotus frontalis LeConte (Coleoptera: Curculionidae) has been identified as a candidate biological control agent for this invasive species. The aims of this study were twofold; to firstly determine the importance of tubers to S. platyphylla populations growing in South Africa; and secondly, to determine the biology and suitability of L. frontalis, a tuber feeder, as a candidate biological control agent. Surveys of S. platyphylla populations in South Africa showed that tubers were found in all sampled sites, except for Krantzkloof Nature reserve in KwaZulu-Natal Province. The highest number of tubers was 97.75 ± 10.62 (SE) m-2 recorded at Jonkershoek in the Western Cape Province. Monthly sampling from two sites in the Eastern Cape Province, the Makana Botanical Gardens and Maden Dam showed that neither season nor water depth affected tuber production. However, the mean number of tubers as well as mass of tubers sampled, were consistently higher (F(1,179) = 20.9542, P < 0.0001) and heavier (F(1, 857) = 585.7293, P < 0.0001) at the Botanical Gardens than at Maden Dam, respectively. The study showed that tubers are an important life stage of S. platyphylla populations and may vary in size and abundance between and within sites. The tuber feeding weevil was shown to develop from egg to ovipositing adult within just over 40 days. Females were recorded to lay up to 48 eggs within a period of one week. Impact studies showed that adult feeding led to a reduction in all but one of the 11 measured plant growth and developmental measurements, including a reduction in the mean mass of the above-ground plant material (F(2,2743) = 12.05, P = 0.002) as well as a reduction in size and abundance of tubers (F(2,58.47) = 9.756, P = 0.0006) and stolons(F(14.943) = 8.7577, P = 0.003). These results are encouraging and suggest that if the insect is released in South Africa, it may prove to be a valuable biocontrol agent. It is concluded that, until suitable biological control options become available in South Africa, the chemical and mechanical control measures currently implemented should continue, however, controlling tubers should be considered during the planning and implementation of these strategies. , Thesis (MSc) -- Faculty of Science, Zoology and Entomology, 2021
- Full Text:
- Date Issued: 2021-10
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
The biological control of aquatic weeds in South Africa: current status and future challenges
- Hill, Martin P, Coetzee, Julie A
- Authors: Hill, Martin P , Coetzee, Julie A
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59909 , vital:27706 , https://doi.org/10.4102/abc.v47i2.2152
- Description: Aquatic ecosystems in South Africa have been prone to invasion by introduced macrophytes since the late 1800s, when water hyacinth, Eichhornia crassipes (Mart.) Solms-Laub. (Pontederiaceae), was first recorded as naturalised in KwaZulu-Natal (Cilliers 1991). Several other species of freshwater aquatic plants, all notorious weeds in other parts of the world, have also become invasive in many of the rivers, man-made impoundments, lakes and wetlands of South Africa (Hill 2003). These are Pistia stratiotes L. (Araceae) (water lettuce); Salvinia molesta D.S. Mitch. (Salviniaceae) (salvinia); Myriophyllum aquaticum (Vell. Conc.) Verd. (parrot's feather); and Azolla filiculoides Lam. (Azollaceae) (red water fern) (Hill 2003), which along with water hyacinth comprise the 'Big Bad Five' (Henderson & Cilliers 2002). Recently, new invasive aquatic plant species have been recorded which are still at their early stages of invasion, including the submerged species, Egeria densa Planch. (Hydrocharitaceae) (Brazilian water weed) and Hydrilla verticillata (L.f.) Royle (Hydrocharitaceae); the emergent species, Sagittaria platyphylla (Engelm.) J.G.Sm. and S. latifolia Willd. (Alismataceae); Lythrum salicaria L. (Lythraceae) (purple loosestrife), Nasturtium officinale W.T. Aiton. (Brassicaceae) (watercress); Iris pseudacorus L. (Iridaceae) (yellow flag); and Hydrocleys nymphoides (Humb. & Bonpl. ex Willd.) Buchenau (Alismataceae) (water poppy); and the new floating weeds, Salvinia minima Baker (Salviniaceae) and Azolla cristata Kaulf. (Azollaceae) (Mexican azolla); and the rooted floating Nymphaea mexicana Zucc. (Nymphaeceae) (Mexican water lily) (Coetzee et al. 2011a; Coetzee, Bownes & Martin 2011b). The mode of introduction of these species is mainly through the horticultural and aquarium trade (Martin & Coetzee 2011), and two issues contribute to the invasiveness of these macrophytes following establishment: the lack of co-evolved natural enemies in their adventive range (McFadyen 1998); and disturbance, the presence of nitrate- and phosphate-enriched waters, associated with urban, agricultural and industrial pollution that promotes plant growth (Coetzee & Hill 2012).
- Full Text:
- Date Issued: 2017
- Authors: Hill, Martin P , Coetzee, Julie A
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59909 , vital:27706 , https://doi.org/10.4102/abc.v47i2.2152
- Description: Aquatic ecosystems in South Africa have been prone to invasion by introduced macrophytes since the late 1800s, when water hyacinth, Eichhornia crassipes (Mart.) Solms-Laub. (Pontederiaceae), was first recorded as naturalised in KwaZulu-Natal (Cilliers 1991). Several other species of freshwater aquatic plants, all notorious weeds in other parts of the world, have also become invasive in many of the rivers, man-made impoundments, lakes and wetlands of South Africa (Hill 2003). These are Pistia stratiotes L. (Araceae) (water lettuce); Salvinia molesta D.S. Mitch. (Salviniaceae) (salvinia); Myriophyllum aquaticum (Vell. Conc.) Verd. (parrot's feather); and Azolla filiculoides Lam. (Azollaceae) (red water fern) (Hill 2003), which along with water hyacinth comprise the 'Big Bad Five' (Henderson & Cilliers 2002). Recently, new invasive aquatic plant species have been recorded which are still at their early stages of invasion, including the submerged species, Egeria densa Planch. (Hydrocharitaceae) (Brazilian water weed) and Hydrilla verticillata (L.f.) Royle (Hydrocharitaceae); the emergent species, Sagittaria platyphylla (Engelm.) J.G.Sm. and S. latifolia Willd. (Alismataceae); Lythrum salicaria L. (Lythraceae) (purple loosestrife), Nasturtium officinale W.T. Aiton. (Brassicaceae) (watercress); Iris pseudacorus L. (Iridaceae) (yellow flag); and Hydrocleys nymphoides (Humb. & Bonpl. ex Willd.) Buchenau (Alismataceae) (water poppy); and the new floating weeds, Salvinia minima Baker (Salviniaceae) and Azolla cristata Kaulf. (Azollaceae) (Mexican azolla); and the rooted floating Nymphaea mexicana Zucc. (Nymphaeceae) (Mexican water lily) (Coetzee et al. 2011a; Coetzee, Bownes & Martin 2011b). The mode of introduction of these species is mainly through the horticultural and aquarium trade (Martin & Coetzee 2011), and two issues contribute to the invasiveness of these macrophytes following establishment: the lack of co-evolved natural enemies in their adventive range (McFadyen 1998); and disturbance, the presence of nitrate- and phosphate-enriched waters, associated with urban, agricultural and industrial pollution that promotes plant growth (Coetzee & Hill 2012).
- Full Text:
- Date Issued: 2017
The establishment and rapid spread of Sagittaria Platyphylla in South Africa:
- Ndlovu, Mpilonhle S, Coetzee, Julie A, Nxumalo, Menzi M, Lalla, Reshnee, Shabalala, Ntombifuthi, Martin, Grant D
- Authors: Ndlovu, Mpilonhle S , Coetzee, Julie A , Nxumalo, Menzi M , Lalla, Reshnee , Shabalala, Ntombifuthi , Martin, Grant D
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/149788 , vital:38884 , https://doi.org/10.3390/w12051472
- Description: Sagittaria platyphylla Engelm. (Alismataceae) is a freshwater aquatic macrophyte that has become an important invasive weed in freshwater systems in South Africa, New Zealand, Australia, and recently China. In South Africa, due to its rapid increase in distribution and ineffective control options, it is recognised as one of the country’s worst invasive aquatic alien plants. In this paper, we investigate the spread of the plant since its first detection in 2008, and the management strategies currently carried out against it. Despite early detection and rapid response programmes, which included chemical and mechanical control measures, the plant was able to spread both within and between sites, increasing from just one site in 2008 to 72 by 2019. Once introduced into a lotic system, the plant was able to spread rapidly, in some cases up to 120 km within 6 years, with an average of 10 km per year. The plant was successfully extirpated at some sites, however, due to the failure of chemical and mechanical control, biological control is currently being considered as a potential control option.
- Full Text:
- Date Issued: 2020
- Authors: Ndlovu, Mpilonhle S , Coetzee, Julie A , Nxumalo, Menzi M , Lalla, Reshnee , Shabalala, Ntombifuthi , Martin, Grant D
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/149788 , vital:38884 , https://doi.org/10.3390/w12051472
- Description: Sagittaria platyphylla Engelm. (Alismataceae) is a freshwater aquatic macrophyte that has become an important invasive weed in freshwater systems in South Africa, New Zealand, Australia, and recently China. In South Africa, due to its rapid increase in distribution and ineffective control options, it is recognised as one of the country’s worst invasive aquatic alien plants. In this paper, we investigate the spread of the plant since its first detection in 2008, and the management strategies currently carried out against it. Despite early detection and rapid response programmes, which included chemical and mechanical control measures, the plant was able to spread both within and between sites, increasing from just one site in 2008 to 72 by 2019. Once introduced into a lotic system, the plant was able to spread rapidly, in some cases up to 120 km within 6 years, with an average of 10 km per year. The plant was successfully extirpated at some sites, however, due to the failure of chemical and mechanical control, biological control is currently being considered as a potential control option.
- Full Text:
- Date Issued: 2020
Mechanistic studies of unusual Miruta-Baylis-Hillman reactions
- Authors: Nyoni, Dubekile
- Date: 2012
- Subjects: Chemical reactions Benzaldehyde Acrylonitrile Methyl acrylate Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4400 , http://hdl.handle.net/10962/d1006692
- Description: This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.
- Full Text:
- Date Issued: 2012
- Authors: Nyoni, Dubekile
- Date: 2012
- Subjects: Chemical reactions Benzaldehyde Acrylonitrile Methyl acrylate Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4400 , http://hdl.handle.net/10962/d1006692
- Description: This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.
- Full Text:
- Date Issued: 2012
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 palladium nanoparticles for radiopharmaceutical application
- Authors: Gandidzanwa, Sendibitiyosi
- Date: 2019
- Subjects: Nanotechnology , Nanostructures Nanofluids
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/42163 , vital:36631
- Description: The dissertation describes an in-depth synthesis and optimisation of palladium(0) nanoparticles of three distinct size ranges, respective capping agents, and cellular uptake studies using a non-toxic concentration (10 μM), laying a foundation for the design of palladium-based folate receptor-targeted theranostic nanoradiopharmaceutical. In the preliminary selection to determine the optimal diamines for the study, ethylenediamine, hexamethylenediamine, 1,10-diaminodecane, 1,12-diaminododecane, 1,4- diaminobenzene, 4,4’-ethylenedianiline, 1,2-diphenyl-1,2-diaminoethane, and tetraaminophthalocyanine were employed. The characterisation of the nanoparticles obtained from the in situ reduction of palladium(II) salt at room temperature by either 1,2,3- trihydroxybenze (pyrogallol), citric acid, sodium metabisulphite, sodium borohydride, hydrazine hydrate, or formaldehyde was performed. Ethylenediamine and sodium borohydride were found to be the best diamine capping and reducing agent, respectively. Systematic investigations determined that the nanoparticle synthesis was dependent on various reaction parameters: such as reaction temperature, time, reductant reducing power, and capping agents. The parameters effects on the nanoparticle size, morphology, shape, stability, crystallinity, and surface charge were investigated. The optical properties, elemental composition, functional group, concentration and molecular weight for the synthesised nanoparticles or conjugates were determined. These properties were analysed using Ultraviolet–visible spectroscopy (UV-Vis), high resolution transmission electron microscopy (HRTEM) coupled with selective area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), zeta potential (ZP), dynamic light scattering (DLS), elemental analysis (EA), 1H and 13C-nuclear magnetic resonance (1H- and 13CNMR), Fourier-transform infrared spectroscopy (FTIR), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and liquid chromatography-mass spectroscopy (LC-MS). The in vitro cytotoxicity, cell uptake, and internalisation studies of palladium nanoparticles (10 μM) ranging in size and different types of capping agent were performed using three breast cancer cell lines: MDA-MB-468 , MCF-7 and MDA-MB-231 , and a non-tumorigenic MCF-10A breast cell line. The cell uptake and internalisation were investigated using ICP-OES and TEM. A high dependence between reduction rate and concentration of palladium precursor was observed for the room temperature synthesis of palladium nanoparticles, and the employed synthesis procedure will be applied to the hot palladium isotope (109Pd). A facile, green, aqueous synthesis route for palladium nanoparticles at room temperature was developed, and the synthesised nanoparticles indicated narrow size distributions. A concentration dependence between cytotoxicity and palladium nanoparticles was observed, with lower concentrations (10 μM) exhibiting minimal cytotoxicity relative to higher concentrations (100 μM). The cellular uptake of palladium nanoparticles was found to be concentration, folate-receptor, capping agent, and cell line proliferation-dependent. Well-defined, monodispersed, and negatively charged folate-ethylenediamine and folate-phthalocyanine capped palladium nanoparticles were taken up by cells, with higher nanoparticle internalisation in folate receptor positive tumorigenic cells relative to folate receptor negative non-tumorigenic cells. It can be concluded that palladium(0) nanoparticles can be synthesised from the reduction of palladium(II) by sodium borohydride at room temperature. The folate-conjugated palladium nanoparticles are non-cytotoxic at 10 μM and were successfully optimised and selectively delivered to folate receptor-positive breast cancer cells (MDA-MB-231 and MCF-7) relative to non-tumorigenic breast cells (MCF-10A) and folate receptor negative cancer cells (MDA-MB-468).
- Full Text:
- Date Issued: 2019
- Authors: Gandidzanwa, Sendibitiyosi
- Date: 2019
- Subjects: Nanotechnology , Nanostructures Nanofluids
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/42163 , vital:36631
- Description: The dissertation describes an in-depth synthesis and optimisation of palladium(0) nanoparticles of three distinct size ranges, respective capping agents, and cellular uptake studies using a non-toxic concentration (10 μM), laying a foundation for the design of palladium-based folate receptor-targeted theranostic nanoradiopharmaceutical. In the preliminary selection to determine the optimal diamines for the study, ethylenediamine, hexamethylenediamine, 1,10-diaminodecane, 1,12-diaminododecane, 1,4- diaminobenzene, 4,4’-ethylenedianiline, 1,2-diphenyl-1,2-diaminoethane, and tetraaminophthalocyanine were employed. The characterisation of the nanoparticles obtained from the in situ reduction of palladium(II) salt at room temperature by either 1,2,3- trihydroxybenze (pyrogallol), citric acid, sodium metabisulphite, sodium borohydride, hydrazine hydrate, or formaldehyde was performed. Ethylenediamine and sodium borohydride were found to be the best diamine capping and reducing agent, respectively. Systematic investigations determined that the nanoparticle synthesis was dependent on various reaction parameters: such as reaction temperature, time, reductant reducing power, and capping agents. The parameters effects on the nanoparticle size, morphology, shape, stability, crystallinity, and surface charge were investigated. The optical properties, elemental composition, functional group, concentration and molecular weight for the synthesised nanoparticles or conjugates were determined. These properties were analysed using Ultraviolet–visible spectroscopy (UV-Vis), high resolution transmission electron microscopy (HRTEM) coupled with selective area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS), X-ray powder diffraction (XRD), zeta potential (ZP), dynamic light scattering (DLS), elemental analysis (EA), 1H and 13C-nuclear magnetic resonance (1H- and 13CNMR), Fourier-transform infrared spectroscopy (FTIR), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and liquid chromatography-mass spectroscopy (LC-MS). The in vitro cytotoxicity, cell uptake, and internalisation studies of palladium nanoparticles (10 μM) ranging in size and different types of capping agent were performed using three breast cancer cell lines: MDA-MB-468 , MCF-7 and MDA-MB-231 , and a non-tumorigenic MCF-10A breast cell line. The cell uptake and internalisation were investigated using ICP-OES and TEM. A high dependence between reduction rate and concentration of palladium precursor was observed for the room temperature synthesis of palladium nanoparticles, and the employed synthesis procedure will be applied to the hot palladium isotope (109Pd). A facile, green, aqueous synthesis route for palladium nanoparticles at room temperature was developed, and the synthesised nanoparticles indicated narrow size distributions. A concentration dependence between cytotoxicity and palladium nanoparticles was observed, with lower concentrations (10 μM) exhibiting minimal cytotoxicity relative to higher concentrations (100 μM). The cellular uptake of palladium nanoparticles was found to be concentration, folate-receptor, capping agent, and cell line proliferation-dependent. Well-defined, monodispersed, and negatively charged folate-ethylenediamine and folate-phthalocyanine capped palladium nanoparticles were taken up by cells, with higher nanoparticle internalisation in folate receptor positive tumorigenic cells relative to folate receptor negative non-tumorigenic cells. It can be concluded that palladium(0) nanoparticles can be synthesised from the reduction of palladium(II) by sodium borohydride at room temperature. The folate-conjugated palladium nanoparticles are non-cytotoxic at 10 μM and were successfully optimised and selectively delivered to folate receptor-positive breast cancer cells (MDA-MB-231 and MCF-7) relative to non-tumorigenic breast cells (MCF-10A) and folate receptor negative cancer cells (MDA-MB-468).
- Full Text:
- Date Issued: 2019
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
Antioxidant and Anticholinesterase Activities of Macrosphyra Longistyla (DC) Hiern Relevant in the Management of Alzheimer's Disease.
- Authors: Oyedeji A O
- Date: 2019
- Subjects: Macrosphyra longistyla; antioxidant; cholinesterase; total flavonoid; total phenolic
- Identifier: http://hdl.handle.net/11260/1504 , vital:37763
- Full Text:
- Authors: Oyedeji A O
- Date: 2019
- Subjects: Macrosphyra longistyla; antioxidant; cholinesterase; total flavonoid; total phenolic
- Identifier: http://hdl.handle.net/11260/1504 , vital:37763
- Full Text:
antioxidants-08-00400 (1) - Dr Elufioye.pdf
- Authors: Oyedeji, Adebola Omowunmi
- Language: English
- Identifier: http://hdl.handle.net/11260/2479 , vital:41899
- Description: Various articles from Prof Adebola Oyedeji
- Full Text:
- Authors: Oyedeji, Adebola Omowunmi
- Language: English
- Identifier: http://hdl.handle.net/11260/2479 , vital:41899
- Description: Various articles from Prof Adebola Oyedeji
- Full Text:
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