Film production incentives, employment transformation and domestic expenditure in South Africa: visualizing subsidy effectiveness
- Collins, Alan, Ishizaka, Alessio, Snowball, Jeanette D
- Authors: Collins, Alan , Ishizaka, Alessio , Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/67456 , vital:29094 , https://doi.org/10.1080/10286632.2016.1255206
- Description: Publisher version , In 2004 the South African Department of Trade and Industry (DTI) introduced a Film and Television Production Rebate Programme. In order to qualify for the rebate, certain criteria have to be met including success in job creation and skills development within the industry, alongside a particular focus on the percentage of ‘historically disadvantaged individuals’ employed. This study sets out the issues associated with evaluating success in meeting these various criteria and is, to the best of our knowledge, the first study to apply multi-criteria visualization techniques to inform the evaluation of public subsidy effectiveness. The ‘PROMETHEE’ method is applied and apart from presenting project performance in a visually intuitive manner, the approach helps to clarify patterns of relative success, show where policy objectives are competing, and to identify project exemplars for more efficiently guiding future public support in the sector.
- Full Text: false
- Date Issued: 2016
- Authors: Collins, Alan , Ishizaka, Alessio , Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/67456 , vital:29094 , https://doi.org/10.1080/10286632.2016.1255206
- Description: Publisher version , In 2004 the South African Department of Trade and Industry (DTI) introduced a Film and Television Production Rebate Programme. In order to qualify for the rebate, certain criteria have to be met including success in job creation and skills development within the industry, alongside a particular focus on the percentage of ‘historically disadvantaged individuals’ employed. This study sets out the issues associated with evaluating success in meeting these various criteria and is, to the best of our knowledge, the first study to apply multi-criteria visualization techniques to inform the evaluation of public subsidy effectiveness. The ‘PROMETHEE’ method is applied and apart from presenting project performance in a visually intuitive manner, the approach helps to clarify patterns of relative success, show where policy objectives are competing, and to identify project exemplars for more efficiently guiding future public support in the sector.
- Full Text: false
- Date Issued: 2016
Towards a framework for assessing the sustainability of local economic development based on natural resources: honeybush tea in the Eastern Cape Province of South Africa
- Polak, James, Snowball, Jeanette D
- Authors: Polak, James , Snowball, Jeanette D
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69201 , vital:29445 , https://doi.org/10.1080/13549839.2016.1196348
- Description: Despite the popularity of local economic development (LED) as a job creation and economic growth strategy in South Africa, many LED projects have not proved to be sustainable in the long-run, especially where human systems interact with biological ones. This article examines the relationship between sustainability and LED within the context of the emerging honeybush tea industry in the Eastern Cape. Data were gathered from provincial as well as local government policy documents and reports, and via key informant interviews. The data were analysed using Connelly’s [(2007). Mapping sustainable development as a contested concept. Local Environment, 12 (3), 259–278] three pronged approach to sustainable development as a lens through which to view the local industry. Findings showed that the industry offers many opportunities for development, including job creation in poorer, rural households; sustainable wild harvesting using a permit system; commercial cultivation; potential to develop social capital; potential for community-based LED; and product diversification. However, there are also corresponding challenges: There is currently no reliable data on the maximum sustainable yield, which is needed to guide quota allocations for entrepreneurial harvesters harvesting from wild stocks; possible biodiversity loss; and enforcing the permit scheme is proving difficult in remote rural areas.
- Full Text: false
- Date Issued: 2017
- Authors: Polak, James , Snowball, Jeanette D
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69201 , vital:29445 , https://doi.org/10.1080/13549839.2016.1196348
- Description: Despite the popularity of local economic development (LED) as a job creation and economic growth strategy in South Africa, many LED projects have not proved to be sustainable in the long-run, especially where human systems interact with biological ones. This article examines the relationship between sustainability and LED within the context of the emerging honeybush tea industry in the Eastern Cape. Data were gathered from provincial as well as local government policy documents and reports, and via key informant interviews. The data were analysed using Connelly’s [(2007). Mapping sustainable development as a contested concept. Local Environment, 12 (3), 259–278] three pronged approach to sustainable development as a lens through which to view the local industry. Findings showed that the industry offers many opportunities for development, including job creation in poorer, rural households; sustainable wild harvesting using a permit system; commercial cultivation; potential to develop social capital; potential for community-based LED; and product diversification. However, there are also corresponding challenges: There is currently no reliable data on the maximum sustainable yield, which is needed to guide quota allocations for entrepreneurial harvesters harvesting from wild stocks; possible biodiversity loss; and enforcing the permit scheme is proving difficult in remote rural areas.
- Full Text: false
- Date Issued: 2017
Employment and diversity in the cultural and creative industries in South Africa: research note
- Authors: Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/71493 , vital:29858 , https://hdl.handle.net/10520/EJC188591
- Description: The publication of Richard Florida's (2002) The Rise of the Creative Class marked a growing international interest in the creative economy. There are several ways of understanding the creative economy, often divided into the cultural and creative industries. Cultural industries are those whose major outputs have some symbolic value, such as fine arts, film and craft, jewelry design, publishing and fashion. Creative industries are defined more broadly as those that have knowledge as their major input. In addition to cultural goods and services, these include things like software design and internet services. UNESCO (2009) provides guidelines for defining the cultural and creative industries and the ways in which they can be measured, but there is currently no international consensus. Nor is there likely to be, since different countries will have very different levels of involvement and focus that may shape what information is useful, for example, for shaping policy.
- Full Text: false
- Date Issued: 2016
- Authors: Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/71493 , vital:29858 , https://hdl.handle.net/10520/EJC188591
- Description: The publication of Richard Florida's (2002) The Rise of the Creative Class marked a growing international interest in the creative economy. There are several ways of understanding the creative economy, often divided into the cultural and creative industries. Cultural industries are those whose major outputs have some symbolic value, such as fine arts, film and craft, jewelry design, publishing and fashion. Creative industries are defined more broadly as those that have knowledge as their major input. In addition to cultural goods and services, these include things like software design and internet services. UNESCO (2009) provides guidelines for defining the cultural and creative industries and the ways in which they can be measured, but there is currently no international consensus. Nor is there likely to be, since different countries will have very different levels of involvement and focus that may shape what information is useful, for example, for shaping policy.
- Full Text: false
- Date Issued: 2016
Water footprint assessment of citrus production in South Africa: A case study of the Lower Sundays River Valley
- Munro, Samantha A, Fraser, Gavin C G, Snowball, Jeanette D, Pahlow, Markus
- Authors: Munro, Samantha A , Fraser, Gavin C G , Snowball, Jeanette D , Pahlow, Markus
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69240 , vital:29463 , https://doi.org/10.1016/j.jclepro.2016.06.142
- Description: Water footprint assessment is a developing method that is being increasingly applied to quantify water use, prioritise reductions, assess sustainability and provide information to achieve sustainable, efficient, and equitable water use. The objectives of this paper were to conduct a water footprint assessment of primary citrus production within the Lower Sundays River Valley in South Africa using local, high-resolution data and to examine indicators (water scarcity, pollution, efficiency, productivity and access) to determine the sustainability of blue, green and grey water footprints of a wet, dry and average year. Lemons were found to have the lowest blue and combined green-blue water footprint per ton of production across all climatic years, followed by soft citrus, valencias and navels. Valencias had the lowest, and navels the highest grey WF (relating to inorganic nitrogen). Lemons, despite their high crop water and fertiliser requirements, were regarded more economically efficient in comparison to valencias, soft citrus and navels, in that they provided higher net income and more employment hours per m3 of water in comparison to other citrus crops. In an average season, lemons generated approximately 39% more income per m3 of water than navels, despite navels being the dominant cultivar. Blue water consumption for citrus in the catchment was calculated to be 58.7 Mm3 for an average season and 89.2 Mm3 for a dry season. Due to an inter-basin transfer scheme, no physical water scarcity occurred, and both environmental and basic human needs are met. Water pollution levels related to nitrogen however, exceeded the assimilative capacity of the run-off in dry years. The area also experiences institutional and infrastructural scarcity and 14% of the population do not have access to piped water. Stakeholders and governments may use the results of water footprint assessments to determine the status of river basins, make evaluations for future water usage and the potential impacts of expanding agriculture and different management strategies. Including environmental and socio-economic indicators will also improve the integrity of water footprint assessments.
- Full Text: false
- Date Issued: 2016
- Authors: Munro, Samantha A , Fraser, Gavin C G , Snowball, Jeanette D , Pahlow, Markus
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69240 , vital:29463 , https://doi.org/10.1016/j.jclepro.2016.06.142
- Description: Water footprint assessment is a developing method that is being increasingly applied to quantify water use, prioritise reductions, assess sustainability and provide information to achieve sustainable, efficient, and equitable water use. The objectives of this paper were to conduct a water footprint assessment of primary citrus production within the Lower Sundays River Valley in South Africa using local, high-resolution data and to examine indicators (water scarcity, pollution, efficiency, productivity and access) to determine the sustainability of blue, green and grey water footprints of a wet, dry and average year. Lemons were found to have the lowest blue and combined green-blue water footprint per ton of production across all climatic years, followed by soft citrus, valencias and navels. Valencias had the lowest, and navels the highest grey WF (relating to inorganic nitrogen). Lemons, despite their high crop water and fertiliser requirements, were regarded more economically efficient in comparison to valencias, soft citrus and navels, in that they provided higher net income and more employment hours per m3 of water in comparison to other citrus crops. In an average season, lemons generated approximately 39% more income per m3 of water than navels, despite navels being the dominant cultivar. Blue water consumption for citrus in the catchment was calculated to be 58.7 Mm3 for an average season and 89.2 Mm3 for a dry season. Due to an inter-basin transfer scheme, no physical water scarcity occurred, and both environmental and basic human needs are met. Water pollution levels related to nitrogen however, exceeded the assimilative capacity of the run-off in dry years. The area also experiences institutional and infrastructural scarcity and 14% of the population do not have access to piped water. Stakeholders and governments may use the results of water footprint assessments to determine the status of river basins, make evaluations for future water usage and the potential impacts of expanding agriculture and different management strategies. Including environmental and socio-economic indicators will also improve the integrity of water footprint assessments.
- Full Text: false
- Date Issued: 2016
The effectiveness and impacts of subsidies to film industries
- Collins, Alan, Snowball, Jeanette D
- Authors: Collins, Alan , Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/68511 , vital:29273 , https://www.southafricanculturalobservatory.org.za/
- Description: Publisher version , Conference paper presented at the South African Cultural Observatory, First National Conference: Counting Culture, The Cultural and Creative Industries in National and International Context, 16-17 May 2016, The Boardwalk International Convention Centre, Nelson Mandela Bay.
- Full Text:
- Date Issued: 2016
- Authors: Collins, Alan , Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/68511 , vital:29273 , https://www.southafricanculturalobservatory.org.za/
- Description: Publisher version , Conference paper presented at the South African Cultural Observatory, First National Conference: Counting Culture, The Cultural and Creative Industries in National and International Context, 16-17 May 2016, The Boardwalk International Convention Centre, Nelson Mandela Bay.
- Full Text:
- Date Issued: 2016
Festival fringe production and the long tail
- Authors: Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/68855 , vital:29332 , http://www.econrsa.org/node/1170
- Description: Publisher version , In the past 15 years, there has been a worldwide proliferation of arts festivals, including so-called "fringe" festivals, which encouraged more experimental and avant-garde productions. While fringe festival productions had the potential to generate significant income for producers, their aims were primarily related to artistic innovation and it is well known that putting on a fringe show is highly unlikely to provide financial gain for most producers. This is what is referred to in statistics and marketing as a "long tail" distribution, in which a minority of producers in a particular market earn the vast majority of industry income. However, for individual producers of live theatre, such a distribution represents high risks and potentially large financial losses. This article uses producer data from two different fringe festivals in South Africa to explore determinants of ticket sales and box-office income. Included in the analysis is a consideration of the impact of genre and pricing strategies on the probability (Logit model) of shows being in the top 10%, 30% and 50% of best-selling and earning productions. Results support the long tail hypothesis.
- Full Text:
- Date Issued: 2016
- Authors: Snowball, Jeanette D
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/68855 , vital:29332 , http://www.econrsa.org/node/1170
- Description: Publisher version , In the past 15 years, there has been a worldwide proliferation of arts festivals, including so-called "fringe" festivals, which encouraged more experimental and avant-garde productions. While fringe festival productions had the potential to generate significant income for producers, their aims were primarily related to artistic innovation and it is well known that putting on a fringe show is highly unlikely to provide financial gain for most producers. This is what is referred to in statistics and marketing as a "long tail" distribution, in which a minority of producers in a particular market earn the vast majority of industry income. However, for individual producers of live theatre, such a distribution represents high risks and potentially large financial losses. This article uses producer data from two different fringe festivals in South Africa to explore determinants of ticket sales and box-office income. Included in the analysis is a consideration of the impact of genre and pricing strategies on the probability (Logit model) of shows being in the top 10%, 30% and 50% of best-selling and earning productions. Results support the long tail hypothesis.
- Full Text:
- Date Issued: 2016
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
Art investment in South Africa: portfolio diversification and art market efficiency
- Botha, Ferdi, Snowball, Jeanette D, Scott, Brett
- Authors: Botha, Ferdi , Snowball, Jeanette D , Scott, Brett
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/64794 , vital:28601 , http://www.dx.doi.org/10.17159/2222-3436/2016/v19n3a4
- Description: Art has been suggested as a good way to diversify investment portfolios during times of financial uncertainty. The argument is that art exhibits different risk and return characteristics to conventional investments in other asset classes. The new Citadel art price index offered the opportunity to test this theory in the South African context. Moreover, this paper tests whether art prices are efficient. The Citadel index uses the hedonic regression method with observations drawn from the top 100, 50 and 20 artists by sales volume, giving approximately 29 503 total auction observations. The Index consists of quarterly data from the period 2000Q1 to 2013Q3. A vector autoregression of the art price index, Johannesburg stock exchange all-share index, house price index, and South African government bond index were used. Results show that, when there are increased returns on the stock market in a preceding period and wealth increases, there is a change in the Citadel art price index in the same direction. No significant difference was found between the house price index and the art price index, or between the art and government bond price indices. The art market is also found to be inefficient, thereby exacerbating the risk of investing in art. Overall, the South African art market does not offer the opportunity to diversify portfolios dominated by either property, bonds, or shares.
- Full Text:
- Date Issued: 2016
- Authors: Botha, Ferdi , Snowball, Jeanette D , Scott, Brett
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/64794 , vital:28601 , http://www.dx.doi.org/10.17159/2222-3436/2016/v19n3a4
- Description: Art has been suggested as a good way to diversify investment portfolios during times of financial uncertainty. The argument is that art exhibits different risk and return characteristics to conventional investments in other asset classes. The new Citadel art price index offered the opportunity to test this theory in the South African context. Moreover, this paper tests whether art prices are efficient. The Citadel index uses the hedonic regression method with observations drawn from the top 100, 50 and 20 artists by sales volume, giving approximately 29 503 total auction observations. The Index consists of quarterly data from the period 2000Q1 to 2013Q3. A vector autoregression of the art price index, Johannesburg stock exchange all-share index, house price index, and South African government bond index were used. Results show that, when there are increased returns on the stock market in a preceding period and wealth increases, there is a change in the Citadel art price index in the same direction. No significant difference was found between the house price index and the art price index, or between the art and government bond price indices. The art market is also found to be inefficient, thereby exacerbating the risk of investing in art. Overall, the South African art market does not offer the opportunity to diversify portfolios dominated by either property, bonds, or shares.
- Full Text:
- Date Issued: 2016
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 lived experience of the post-termination period of long-term psychotherapy
- Steenkamp, Jeanette Gwendoline
- Authors: Steenkamp, Jeanette Gwendoline
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3276 , http://hdl.handle.net/10962/d1021272
- Description: This study aimed to gain insight and understanding into adult clients’ personal lived experiences of the post-termination period of long-term psychotherapy. International research which examines the post-termination phase of psychotherapy has found that this particular lived experience can have both positive and negative consequences for clients’ psychosocial wellbeing. Few recent studies focusing on adult clients’ personal experiences of the post-termination phase could be located and none of these studies were conducted in a non-Western context. The study’s aim was to address this gap in the existing literature by using interpretative-phenomenological analysis (IPA) to explore the lived experience of the post-termination period of long-term psychotherapy for two South African adult clients. Data were collected via individual in-depth semi-structured interviews. Analysis of the data yielded the following themes: Therapy remembered as amazing, but hard work, Vivid memories of therapy retained post-termination, Seeing the therapist differently, Keeping the therapist alive, Being different after therapy, “I started losing all my ground I had gained”, and Resuming the external journey. These findings corroborated and expanded upon existing research in the area.
- Full Text:
- Date Issued: 2016
- Authors: Steenkamp, Jeanette Gwendoline
- Date: 2016
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3276 , http://hdl.handle.net/10962/d1021272
- Description: This study aimed to gain insight and understanding into adult clients’ personal lived experiences of the post-termination period of long-term psychotherapy. International research which examines the post-termination phase of psychotherapy has found that this particular lived experience can have both positive and negative consequences for clients’ psychosocial wellbeing. Few recent studies focusing on adult clients’ personal experiences of the post-termination phase could be located and none of these studies were conducted in a non-Western context. The study’s aim was to address this gap in the existing literature by using interpretative-phenomenological analysis (IPA) to explore the lived experience of the post-termination period of long-term psychotherapy for two South African adult clients. Data were collected via individual in-depth semi-structured interviews. Analysis of the data yielded the following themes: Therapy remembered as amazing, but hard work, Vivid memories of therapy retained post-termination, Seeing the therapist differently, Keeping the therapist alive, Being different after therapy, “I started losing all my ground I had gained”, and Resuming the external journey. These findings corroborated and expanded upon existing research in the area.
- Full Text:
- Date Issued: 2016
Rhenium complexes with multidentate imine-, amine-, thione-, thiol-, hydroxy- and carboxamide chelates
- Authors: Habarurema, Gratien
- Date: 2016
- Subjects: Rhenium Metal complexes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12679 , vital:27106
- Description: This study entails the synthesis, spectroscopic and structural characterization of new rhenium complexes with multidentate imine-, amine-, thione-, thiol-, hydroxy- and carboxamide chelates in various oxidation states. Rhenium(I) and (V) complexes with imidazolidine, pyrimidine and bridging pyridyl derivatives are reported in Chapter 3. The reactions of the potential tridentate N,N,Odonor ligand 2,2'-dipyridylketone (dpk) with trans-[ReOCl3(PPh3)2], (n-Bu4N)[ReOCl4] and trans-[ReOI2(OEt)(PPh3)2] led to the isolation of cis-[ReOCl2(edpm)], cis-[ReOCl2(dpk.OH)] and [ReO3(dpk.OH)] respectively (see Scheme 1). The reaction of (E)-N-((pyridine-2-yl)methylene)benzo[d]thiazol-2-amine (pbt) with trans- [ReOCl3(PPh3)2] produced a mononuclear oxorhenium(V) complex cis- [ReOCl2(epm)(PPh3)]. Both dpk and pbt exhibited a nucleophilic attack by acetonitrile (for Hedpm), water (for dpk) and ethanol (for pbt) leading to chelates that act as uninegative tridentate N,N,O- and bidentate N,O-donor chelates respectively. The reaction of [Re(CO)5Cl] with 2,3-dihydro-2,2-di(pyridin-2-yl)-1H-benzo[d]imidazole (H2dpb), (2,6-diaza-cyclohex-1-enylolonium)2-aza-benzoate (H2den) and 2-(2-(pyridine-2-yl)imidazolidin-2-yl)pyridine (H2pip) (see Scheme 1) gave rise to novel rhenium(I) complexes fac-[Re(CO)3(H2dmb)Cl], fac-[Re(CO)3(Hhdm)] and fac-[Re(CO)3(H2pip)]Cl respectively. The monomeric cationic salt fac-[Re(CO)3(H2salbam)]Br and ligand-bridged dimer fac- (μ-H2salet)[Re(CO)3]2 complexes were formed by the reactions of [Re(CO)5X] (X = Br or Cl) with the potentially heptadentate Schiff base 2,2,2-tris (salicylideneimino)- triethylamine (H3salet; Scheme 2) respectively. The reactions of the potentially hexadentate ligands acting as tridentate monoanionic N,N,O- or N,O,O-donor chelates N1-(3-(2-hydroxy enzylideneamino) propylamino) ethyl)benzylidenepropane-1,3-diamine (H2salpd) and N,N -bis(salicylidene) -3,6-dioxa-1,8-diaminooctane (H2saldane) (Scheme 2) with [Re(CO)5Cl] led to the isolation of the mononuclear and dinuclear complexes fac-[Re(CO)3(Hsaldane)] and fac-(μ-salpd)[Re(CO)3]2 respectively. The reactions of [Re(CO)5Cl] with the tetradentate ligands 2-{[2-hydroxy-3-{[(E)-(2- hydroxyphenyl)-methylidene]amino}propyl)imino]methyl}phenol (H2hmp), 6-((6E)- ((3E)-3-((oxocyclohexa-2,4-dienyl)methyleneamino)-2-hydroxypropylimino)methyl)- cyclohexa-2,4-dienone (H2hcd.H2O) zwitterion and 2-((1E)-1-((E)-3-(2-hydoxyphenylmethylideneamino)propylimino)methyl)phenol (H2hdp) (see Scheme 2) resulted in the formation of the neutral fac-[Re(CO)3(Hamp)], fac-[Re(CO)3(Hhetp)] and fac- [Re(CO)3(Happ)] respectively. The treatment of 2-((3-(2-hydroxybenzylamino)-propylamino)methyl)phenol (H2hbp) with [Re(CO)3Cl] and trans-[ReOCl3(PPh3)2] gave the fac-[Re(CO)3(Hhbp)] and (μ-O)[ReO(hbp)]2 complexes. The reactions of the ligands H2hmp, H2hdp and H2hap (see Scheme 2) with trans-[ReOBr3(PPh3)2] and trans-[ReOI2(OEt)(PPh3)2] produced dinuclear oxo-bridged rhenium(V) complexes (μ-O)[ReO(hmp)]2, [(μ-O)[ReO(hdp)]2 and (μ-O)[ReO(hap)]2 respectively. The neutral and anionic binding modes of thiosemicarbazones to the fac-[Re(CO)3]+, cis- [ReO2]+ and trans-[ReO2]+ cores have been investigated in Chapter 6. The reactions of the potentially tridentate ligand 1-{1-(2- hydroxyphenyl)ethylidene}-4- phenylthiosemicarbazide (H2hpt) (see Scheme 3) with [Re(CO)5Cl], cis-[ReO2I(PPh3)2]cand trans-[ReO2(py)4]Cl led to the isolation of the complexes fac-[Re(CO)3(H2hpt)2]Cl, [Re(hipt)(Hipht)(PPh3)] and trans-[ReO(hpt)(Hhpt)] respectively. The X-ray crystal analysis of the complexes show that the ligand H2hpt exhibits decomposition, thiol-enol tautomerism and a thiolate-iminium zwitterionic process, and coordinates in the neutral form via its thione sulfur and nitrogen and anionic through the azo nitrogen, thiolate sulfur and acetophenolic oxygen. A series of nitrogen-heterocyclic amide-, acid-, thiol- and diol-based ligands as well as their related monomeric rhenium(III) and (V) complexes have also been studied (see Chapter 7). The reaction of N-(2-(pyrazine-2-carboxamido)phenyl)pyrazine-2- carboxamide (H2ppc) (Scheme 3) with trans-[ReOBr3(PPh3)2] yielded the complex trans- [ReBr2(Hppca)(PPh3)2]. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with pyridine-2,6-dicarboxylic acid (H2pda) produced the neutral oxorhenium(V) complexes [ReOX2(epca)(PPh3)]. The treatment of trans-[ReOBr3(PPh3)2] with 2-mercaptopyridine- 3-carboxylic acid (H2mpc) gave rise to the rhenium(III) complex [Re(empc)3(PPh3)]. The reaction of 2,6-bis(hydroxymethyl)pyridine (H2bhp) with trans-[ReOI2(EOt)(PPh3)2], trans-[ReOBr3(PPh3)2] and [Re(CO)5Cl] gave the complexes [ReO(Hbhp)2(PPh3)]I.PPh3, cis-[ReOBr2(Hbhp)(PPh3)] and fac-(μ- O)2[Re(CO)3(Hbhp)]2 respectively. Their X-ray crystal structures indicate that the ligand acts as a bidentate monoanionic N,O-donor chelate leaving a free aliphatic hydroxyl group.
- Full Text:
- Date Issued: 2016
- Authors: Habarurema, Gratien
- Date: 2016
- Subjects: Rhenium Metal complexes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/12679 , vital:27106
- Description: This study entails the synthesis, spectroscopic and structural characterization of new rhenium complexes with multidentate imine-, amine-, thione-, thiol-, hydroxy- and carboxamide chelates in various oxidation states. Rhenium(I) and (V) complexes with imidazolidine, pyrimidine and bridging pyridyl derivatives are reported in Chapter 3. The reactions of the potential tridentate N,N,Odonor ligand 2,2'-dipyridylketone (dpk) with trans-[ReOCl3(PPh3)2], (n-Bu4N)[ReOCl4] and trans-[ReOI2(OEt)(PPh3)2] led to the isolation of cis-[ReOCl2(edpm)], cis-[ReOCl2(dpk.OH)] and [ReO3(dpk.OH)] respectively (see Scheme 1). The reaction of (E)-N-((pyridine-2-yl)methylene)benzo[d]thiazol-2-amine (pbt) with trans- [ReOCl3(PPh3)2] produced a mononuclear oxorhenium(V) complex cis- [ReOCl2(epm)(PPh3)]. Both dpk and pbt exhibited a nucleophilic attack by acetonitrile (for Hedpm), water (for dpk) and ethanol (for pbt) leading to chelates that act as uninegative tridentate N,N,O- and bidentate N,O-donor chelates respectively. The reaction of [Re(CO)5Cl] with 2,3-dihydro-2,2-di(pyridin-2-yl)-1H-benzo[d]imidazole (H2dpb), (2,6-diaza-cyclohex-1-enylolonium)2-aza-benzoate (H2den) and 2-(2-(pyridine-2-yl)imidazolidin-2-yl)pyridine (H2pip) (see Scheme 1) gave rise to novel rhenium(I) complexes fac-[Re(CO)3(H2dmb)Cl], fac-[Re(CO)3(Hhdm)] and fac-[Re(CO)3(H2pip)]Cl respectively. The monomeric cationic salt fac-[Re(CO)3(H2salbam)]Br and ligand-bridged dimer fac- (μ-H2salet)[Re(CO)3]2 complexes were formed by the reactions of [Re(CO)5X] (X = Br or Cl) with the potentially heptadentate Schiff base 2,2,2-tris (salicylideneimino)- triethylamine (H3salet; Scheme 2) respectively. The reactions of the potentially hexadentate ligands acting as tridentate monoanionic N,N,O- or N,O,O-donor chelates N1-(3-(2-hydroxy enzylideneamino) propylamino) ethyl)benzylidenepropane-1,3-diamine (H2salpd) and N,N -bis(salicylidene) -3,6-dioxa-1,8-diaminooctane (H2saldane) (Scheme 2) with [Re(CO)5Cl] led to the isolation of the mononuclear and dinuclear complexes fac-[Re(CO)3(Hsaldane)] and fac-(μ-salpd)[Re(CO)3]2 respectively. The reactions of [Re(CO)5Cl] with the tetradentate ligands 2-{[2-hydroxy-3-{[(E)-(2- hydroxyphenyl)-methylidene]amino}propyl)imino]methyl}phenol (H2hmp), 6-((6E)- ((3E)-3-((oxocyclohexa-2,4-dienyl)methyleneamino)-2-hydroxypropylimino)methyl)- cyclohexa-2,4-dienone (H2hcd.H2O) zwitterion and 2-((1E)-1-((E)-3-(2-hydoxyphenylmethylideneamino)propylimino)methyl)phenol (H2hdp) (see Scheme 2) resulted in the formation of the neutral fac-[Re(CO)3(Hamp)], fac-[Re(CO)3(Hhetp)] and fac- [Re(CO)3(Happ)] respectively. The treatment of 2-((3-(2-hydroxybenzylamino)-propylamino)methyl)phenol (H2hbp) with [Re(CO)3Cl] and trans-[ReOCl3(PPh3)2] gave the fac-[Re(CO)3(Hhbp)] and (μ-O)[ReO(hbp)]2 complexes. The reactions of the ligands H2hmp, H2hdp and H2hap (see Scheme 2) with trans-[ReOBr3(PPh3)2] and trans-[ReOI2(OEt)(PPh3)2] produced dinuclear oxo-bridged rhenium(V) complexes (μ-O)[ReO(hmp)]2, [(μ-O)[ReO(hdp)]2 and (μ-O)[ReO(hap)]2 respectively. The neutral and anionic binding modes of thiosemicarbazones to the fac-[Re(CO)3]+, cis- [ReO2]+ and trans-[ReO2]+ cores have been investigated in Chapter 6. The reactions of the potentially tridentate ligand 1-{1-(2- hydroxyphenyl)ethylidene}-4- phenylthiosemicarbazide (H2hpt) (see Scheme 3) with [Re(CO)5Cl], cis-[ReO2I(PPh3)2]cand trans-[ReO2(py)4]Cl led to the isolation of the complexes fac-[Re(CO)3(H2hpt)2]Cl, [Re(hipt)(Hipht)(PPh3)] and trans-[ReO(hpt)(Hhpt)] respectively. The X-ray crystal analysis of the complexes show that the ligand H2hpt exhibits decomposition, thiol-enol tautomerism and a thiolate-iminium zwitterionic process, and coordinates in the neutral form via its thione sulfur and nitrogen and anionic through the azo nitrogen, thiolate sulfur and acetophenolic oxygen. A series of nitrogen-heterocyclic amide-, acid-, thiol- and diol-based ligands as well as their related monomeric rhenium(III) and (V) complexes have also been studied (see Chapter 7). The reaction of N-(2-(pyrazine-2-carboxamido)phenyl)pyrazine-2- carboxamide (H2ppc) (Scheme 3) with trans-[ReOBr3(PPh3)2] yielded the complex trans- [ReBr2(Hppca)(PPh3)2]. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with pyridine-2,6-dicarboxylic acid (H2pda) produced the neutral oxorhenium(V) complexes [ReOX2(epca)(PPh3)]. The treatment of trans-[ReOBr3(PPh3)2] with 2-mercaptopyridine- 3-carboxylic acid (H2mpc) gave rise to the rhenium(III) complex [Re(empc)3(PPh3)]. The reaction of 2,6-bis(hydroxymethyl)pyridine (H2bhp) with trans-[ReOI2(EOt)(PPh3)2], trans-[ReOBr3(PPh3)2] and [Re(CO)5Cl] gave the complexes [ReO(Hbhp)2(PPh3)]I.PPh3, cis-[ReOBr2(Hbhp)(PPh3)] and fac-(μ- O)2[Re(CO)3(Hbhp)]2 respectively. Their X-ray crystal structures indicate that the ligand acts as a bidentate monoanionic N,O-donor chelate leaving a free aliphatic hydroxyl group.
- Full Text:
- Date Issued: 2016
NMMU students' perceptions of their creativity
- Authors: Rogers, Angela Louise
- Date: 2016
- Subjects: Creative ability in business , Creative thinking , Educational innovations
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: http://hdl.handle.net/10948/8037 , vital:24478
- Description: Creativity is seen as the driving force behind innovation. It can even be said to be the same process. It is critical to implement the creativity in order for innovation to actually take place. This combination of creativity and innovation is required for economic growth, sustainability, continuous improvement and competitive edge for organisations. Creativity is more than just artistic ability but includes scientific and problem solving steps and basic everyday creativity. This combination would be key in government departments, organisations and universities today. People’s perception on creativity could hamper their growth and development in this key area, not only for themselves but of others that they come into contact with. People’s perception on creativity is that it is either a genius form in either artistic or musical terms or it is not at all creative. They do not necessarily view the everyday tasks as creative. The research approach for this study is positivistic and deductive. The students’ perception of creativity is gathered using a quantitative questionnaire, where they rank their perceptions. The questionnaire was from an international study and it was made available to all students at the Nelson Mandela Metropolitan University. The data analysis will be both descriptive and inferential in nature. The research seeks to examine students’ perception of their own creativity and how they rate various creative products or services. Students are on their way to the pinnacle in their fields and the creativity should therefore be at its peak to be able to take full advantage and to get maximum benefit from it. The research will gain insight into their perception via a questionnaire where they need to rate themselves. The literature review will investigate creativity, innovation and the links between them. It will analyse the importance of innovation to business and the unlocking of creativity. There are many differing ways to unlock and stimulate creativity and some of these are addressed.
- Full Text:
- Date Issued: 2016
- Authors: Rogers, Angela Louise
- Date: 2016
- Subjects: Creative ability in business , Creative thinking , Educational innovations
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: http://hdl.handle.net/10948/8037 , vital:24478
- Description: Creativity is seen as the driving force behind innovation. It can even be said to be the same process. It is critical to implement the creativity in order for innovation to actually take place. This combination of creativity and innovation is required for economic growth, sustainability, continuous improvement and competitive edge for organisations. Creativity is more than just artistic ability but includes scientific and problem solving steps and basic everyday creativity. This combination would be key in government departments, organisations and universities today. People’s perception on creativity could hamper their growth and development in this key area, not only for themselves but of others that they come into contact with. People’s perception on creativity is that it is either a genius form in either artistic or musical terms or it is not at all creative. They do not necessarily view the everyday tasks as creative. The research approach for this study is positivistic and deductive. The students’ perception of creativity is gathered using a quantitative questionnaire, where they rank their perceptions. The questionnaire was from an international study and it was made available to all students at the Nelson Mandela Metropolitan University. The data analysis will be both descriptive and inferential in nature. The research seeks to examine students’ perception of their own creativity and how they rate various creative products or services. Students are on their way to the pinnacle in their fields and the creativity should therefore be at its peak to be able to take full advantage and to get maximum benefit from it. The research will gain insight into their perception via a questionnaire where they need to rate themselves. The literature review will investigate creativity, innovation and the links between them. It will analyse the importance of innovation to business and the unlocking of creativity. There are many differing ways to unlock and stimulate creativity and some of these are addressed.
- Full Text:
- Date Issued: 2016
Classical and quantum picture of the interior of two-dimensional black holes
- Authors: Shawa, Mark
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3629 , vital:20531
- Description: A quantum-mechanical description of black holes would represent the final step in our understanding of the nature of space-time. However, any progress towards that end is usually foiled by persistent space-time singularities that exist at the center of black holes. From the four-dimensional point of view, black holes seem to resist quantization. Under highly symmetric conditions, all higher-dimensional black holes are two-dimensional. Unlike their higher-dimensional counterparts, two dimensional black holes may not resist quantization. A non-trivial description of gravity in two dimensions is not possible using Einstein’s theory of gravity alone. However, we may still arrive at a consistent description of gravity by introducing a scalar field known as the dilaton. In this thesis, we study both the classical and quantum aspects of the interior of two-dimensional black holes using a generalized dilaton-gravity theory. Classically, we will find that the interior of most two-dimensional black holes is not much different from that of four-dimensional black holes. But by introducing quantized matter into the theory, the fluctuations in space-time will give a different picture of the structure of interior of black holes. Using a low-energy effective field theory, we will show that it is indeed possible to identify quantum modes in the interior of black holes and perform quantum-mechanical calculations near the singularity.
- Full Text:
- Date Issued: 2016
- Authors: Shawa, Mark
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3629 , vital:20531
- Description: A quantum-mechanical description of black holes would represent the final step in our understanding of the nature of space-time. However, any progress towards that end is usually foiled by persistent space-time singularities that exist at the center of black holes. From the four-dimensional point of view, black holes seem to resist quantization. Under highly symmetric conditions, all higher-dimensional black holes are two-dimensional. Unlike their higher-dimensional counterparts, two dimensional black holes may not resist quantization. A non-trivial description of gravity in two dimensions is not possible using Einstein’s theory of gravity alone. However, we may still arrive at a consistent description of gravity by introducing a scalar field known as the dilaton. In this thesis, we study both the classical and quantum aspects of the interior of two-dimensional black holes using a generalized dilaton-gravity theory. Classically, we will find that the interior of most two-dimensional black holes is not much different from that of four-dimensional black holes. But by introducing quantized matter into the theory, the fluctuations in space-time will give a different picture of the structure of interior of black holes. Using a low-energy effective field theory, we will show that it is indeed possible to identify quantum modes in the interior of black holes and perform quantum-mechanical calculations near the singularity.
- Full Text:
- Date Issued: 2016
Investigating the effectiveness of microcatchments at enhancing transplant performance in Nama-Karoo riparian ecosystem restoration
- Jackson, Andrew St. John, Wigley, Benjamin, Schumann, Bonnie, Currie, Bianca
- Authors: Jackson, Andrew St. John , Wigley, Benjamin , Schumann, Bonnie , Currie, Bianca
- Date: 2016
- Subjects: Arid regions agriculture , Environmental degradation , Range ecology
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/7469 , vital:21782
- Description: Globally agricultural rangelands have been subjected to degradation through over-utilization. The loss of productivity of agricultural rangelands around the world has led to the development of methods to restore the productivity of these areas. In South Africa, extensive areas of the Nama-Karoo have been degraded or transformed due in part to unsustainable agricultural activities. The development of restoration methods which are easily implementable and financially viable could increase the probability of stakeholders implementing restoration activities on privately owned land. The removal of the degrading factor is not sufficient to reverse the degradative trend in dryland environments. Active measures must be implemented to arrest the degradation cascade. The climatic conditions of the rangelands of South Africa are limiting to plant performance and the favourable conditions are sporadic. The translocation of plants should be combined with the amelioration of the local conditions. This study tested the restoration technique of microcatchments in association with plant translocation. The effects of microcatchments and planting combinations which were best suited to the survival and performance of the transplants were determined through a field trail. The results showed that microcatchments created microsites which were conducive to transplant survival and growth, including nutrient accumulation and increased soil moisture. The success of the method was dependent on the planting combination used. Plants which are adapted to inundation and the saline conditions of the site performed better. Plants which were older at the time of translocation had higher survival rates than younger transplants. In the conditions of this site, planting adjacent to the microcatchments was necessary to avoid inundation induced mortalities. The environmental conditions of the Nama-Karoo necessitate the coordination of restoration activities with the predicted favourable conditions in order to improve the success of restoration activities.
- Full Text:
- Date Issued: 2016
- Authors: Jackson, Andrew St. John , Wigley, Benjamin , Schumann, Bonnie , Currie, Bianca
- Date: 2016
- Subjects: Arid regions agriculture , Environmental degradation , Range ecology
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: http://hdl.handle.net/10948/7469 , vital:21782
- Description: Globally agricultural rangelands have been subjected to degradation through over-utilization. The loss of productivity of agricultural rangelands around the world has led to the development of methods to restore the productivity of these areas. In South Africa, extensive areas of the Nama-Karoo have been degraded or transformed due in part to unsustainable agricultural activities. The development of restoration methods which are easily implementable and financially viable could increase the probability of stakeholders implementing restoration activities on privately owned land. The removal of the degrading factor is not sufficient to reverse the degradative trend in dryland environments. Active measures must be implemented to arrest the degradation cascade. The climatic conditions of the rangelands of South Africa are limiting to plant performance and the favourable conditions are sporadic. The translocation of plants should be combined with the amelioration of the local conditions. This study tested the restoration technique of microcatchments in association with plant translocation. The effects of microcatchments and planting combinations which were best suited to the survival and performance of the transplants were determined through a field trail. The results showed that microcatchments created microsites which were conducive to transplant survival and growth, including nutrient accumulation and increased soil moisture. The success of the method was dependent on the planting combination used. Plants which are adapted to inundation and the saline conditions of the site performed better. Plants which were older at the time of translocation had higher survival rates than younger transplants. In the conditions of this site, planting adjacent to the microcatchments was necessary to avoid inundation induced mortalities. The environmental conditions of the Nama-Karoo necessitate the coordination of restoration activities with the predicted favourable conditions in order to improve the success of restoration activities.
- Full Text:
- Date Issued: 2016
The emergence of the South African farm crime novel : socio-historical crimes, personal crimes, and the figure of the dog
- Authors: Naidu, Samantha
- Date: 2016
- Language: English
- Type: Article
- Identifier: vital:26325 , http://hdl.handle.net/10962/53776 , https://www.ajol.info/index.php/eia/article/view/142930 , https://orcid.org/0000-0001-9456-8657
- Description: Crime fiction is an established and popular literary genre in South Africa that has gained international recognition and acclaim. The genre continues to expand and develop in terms of thematic concerns and experiments in form. One such notable development is the farm crime novel, which extends the tradition of the South African plaasroman. Recent texts, such as Elaine Proctor’s The Savage Hour and Karin Brynard’s Weeping Waters, quite deliberately set their respective murder mysteries on remote farms, and both novels particularise details of farm life. This article argues that the main concerns of the farm crime novel are, on one level, socio-historical – that is, the crimes perpetrated are the result of relationships to the land, land claims and land re-distribution, and the complex, evolving relationship between landowner and labourer. On another level, true to the conventions of crime fiction, the farm crime novel also explores interpersonal or intimate relationships that result in crimes of passion. Of particular interest is the observation that common to both thematic levels is a profound rendering of the link between human-animal relations and human-human relations. Drawing on Karla Armbruster’s work on the cultural significance of narratives about dogs and the need for more just and ethical relationships with animals, the article then demonstrates how this rendering occurs, often, through the figure of the dog. To conclude, some comments are offered on the position of the farm crime novel in a post-apartheid literary landscape
- Full Text:
- Date Issued: 2016
- Authors: Naidu, Samantha
- Date: 2016
- Language: English
- Type: Article
- Identifier: vital:26325 , http://hdl.handle.net/10962/53776 , https://www.ajol.info/index.php/eia/article/view/142930 , https://orcid.org/0000-0001-9456-8657
- Description: Crime fiction is an established and popular literary genre in South Africa that has gained international recognition and acclaim. The genre continues to expand and develop in terms of thematic concerns and experiments in form. One such notable development is the farm crime novel, which extends the tradition of the South African plaasroman. Recent texts, such as Elaine Proctor’s The Savage Hour and Karin Brynard’s Weeping Waters, quite deliberately set their respective murder mysteries on remote farms, and both novels particularise details of farm life. This article argues that the main concerns of the farm crime novel are, on one level, socio-historical – that is, the crimes perpetrated are the result of relationships to the land, land claims and land re-distribution, and the complex, evolving relationship between landowner and labourer. On another level, true to the conventions of crime fiction, the farm crime novel also explores interpersonal or intimate relationships that result in crimes of passion. Of particular interest is the observation that common to both thematic levels is a profound rendering of the link between human-animal relations and human-human relations. Drawing on Karla Armbruster’s work on the cultural significance of narratives about dogs and the need for more just and ethical relationships with animals, the article then demonstrates how this rendering occurs, often, through the figure of the dog. To conclude, some comments are offered on the position of the farm crime novel in a post-apartheid literary landscape
- Full Text:
- Date Issued: 2016
Development of Palladium selective reagents and materials
- Authors: Moyo, Cyprian Bertrand
- Date: 2016
- Subjects: Palladium Palladium compounds -- Industrial applications Chemistry, Inorganic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/12231 , vital:27046
- Description: The adsorption and separation of Pd(II) from Pt(IV), Ir(IV) and Rh(III) by silica microparticles functionalized with triethylenetetramine (TETA), 2-(2-aminoethylthio)ethanamine (NSN) and 2-(2-(2-aminoethyl)ethylthio)ethanamine (NSSN) in 1 M hydrochloric acid medium was investigated by continuous column studies. The functionalized sorbent materials were characterized by microanalysis, SEM-EDS and FT-IR. Palladium selectivity of the sorbent materials was achieved by stripping of rhodium, iridium and platinum chlorido species with 0.5 M of NaClO4 in 1 M HCl while [PdCl4]2 was eluted with 3% w/v thiourea. The desorption efficiency of thiourea was confirmed by the SEM-EDS analysis of the materials after Pd(II) elution. Palladium loading capacity of the sorbents were in the order S-NSSN (23.85 mg/g) > S-NSN (12.70 mg/g) > S-TETA (4.97 mg/g). The extraction patterns on the sorbent materials were explained by considering the coordination chemistry of the ligand with [PdCl4]2ˉ and ionic interactions of [PtCl6]2ˉ and [IrCl5(H2O]ˉ. The square planar complexes, [Pd(HNSSNH)Cl2]Cl2 and [Pd(NSNH)Cl2][PdCl4]2, were isolated, analyzed by spectroscopy and single crystal X-ray, whereas evidence of the fraction of Pd(II)-TETA complex was obtained by HPLC studies. This provided proof of the inner sphere coordination mechanism as the mode of interaction of these ligands with [PdCl4]2ˉ. Trace amounts of Brˉ anions in ligands resulted in the inadvertent isolation of bromide coordinated Pd(II) NSN and NSSN complexes. The ion-pair salts of [TETAH4]4+ with [PtCl6]2ˉ, [IrCl6]3ˉ and [RhCl6]3ˉ were also isolated and characterized by microanalysis and IR to further explain the extraction patterns.
- Full Text:
- Date Issued: 2016
- Authors: Moyo, Cyprian Bertrand
- Date: 2016
- Subjects: Palladium Palladium compounds -- Industrial applications Chemistry, Inorganic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/12231 , vital:27046
- Description: The adsorption and separation of Pd(II) from Pt(IV), Ir(IV) and Rh(III) by silica microparticles functionalized with triethylenetetramine (TETA), 2-(2-aminoethylthio)ethanamine (NSN) and 2-(2-(2-aminoethyl)ethylthio)ethanamine (NSSN) in 1 M hydrochloric acid medium was investigated by continuous column studies. The functionalized sorbent materials were characterized by microanalysis, SEM-EDS and FT-IR. Palladium selectivity of the sorbent materials was achieved by stripping of rhodium, iridium and platinum chlorido species with 0.5 M of NaClO4 in 1 M HCl while [PdCl4]2 was eluted with 3% w/v thiourea. The desorption efficiency of thiourea was confirmed by the SEM-EDS analysis of the materials after Pd(II) elution. Palladium loading capacity of the sorbents were in the order S-NSSN (23.85 mg/g) > S-NSN (12.70 mg/g) > S-TETA (4.97 mg/g). The extraction patterns on the sorbent materials were explained by considering the coordination chemistry of the ligand with [PdCl4]2ˉ and ionic interactions of [PtCl6]2ˉ and [IrCl5(H2O]ˉ. The square planar complexes, [Pd(HNSSNH)Cl2]Cl2 and [Pd(NSNH)Cl2][PdCl4]2, were isolated, analyzed by spectroscopy and single crystal X-ray, whereas evidence of the fraction of Pd(II)-TETA complex was obtained by HPLC studies. This provided proof of the inner sphere coordination mechanism as the mode of interaction of these ligands with [PdCl4]2ˉ. Trace amounts of Brˉ anions in ligands resulted in the inadvertent isolation of bromide coordinated Pd(II) NSN and NSSN complexes. The ion-pair salts of [TETAH4]4+ with [PtCl6]2ˉ, [IrCl6]3ˉ and [RhCl6]3ˉ were also isolated and characterized by microanalysis and IR to further explain the extraction patterns.
- Full Text:
- Date Issued: 2016
Modelling dispersal processes in impala-cheetah-lion ecosystems with infection in the lions
- Authors: Mbava, Willard
- Date: 2016
- Subjects: Predation (Biology) -- South Africa -- Kruger National Park Endangered species -- South Africa -- Kruger National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11782 , vital:26968
- Description: The study involved the predator-prey interaction of three species namely the predator (Cheetah Acinonyx jubatus), the super-predator (Lion Panthera leo), and their common prey (Impala Aepyceros melampus). The study area is the Kruger National Park. The predator being an endangered species, faces a survival problem. It is frequently killed by the super-predator to reduce competition for prey. The super-predator also scares away the predator o_ its kills. The prey forms the main diet of the predator. The plight of the predator motivated the author to formulate disease and reaction-diffusion models for the species interactions. The purpose of the models were to predict and explain the effect of large competition from the super-predator on the predator population. Important parameters related to additional predator mortality due to presence of super-predator, the disease incidence rate and induced death rate formed the focal points of the analysis. The dynamics of a predator-prey model with disease in super-predator were investigated. The super-predator species is infected with bovine Tuberculosis. In the study, the disease is considered as biological control to allow the predator population to regain from low numbers. The results highlight that in the absence of additional mortality on the predator by the super-predator, the predator population survives extinction. Furthermore, at current levels of disease incidence, the super-predator population is wiped out by the disease. However, the super-predator population survives extinction if the disease incidence rate is low. Persistence of all populations is possible in the case of low disease incidence rate and no additional mortality imparted on the predator. Furthermore, a two-species subsystem, prey and predator, is considered as a special case to determine the effect of super-predator removal from the system, on the survival of the predator. This is treated as a contrasting case from the smaller parks. The results show that the predator population thrives well in the total absence of its main competitor, with its population rising to at least twice the initial value. A reaction-diffusion three-species predator-prey model was formulated and analysed. Stability of the temporal and the spatio-temporal systems, existence and non-existence of stationary steady state solutions were studied. Conditions for the emergence of stationary patterns were deduced. The results show that by choosing the diffusion coeffcient d2 > _D 2 suffciently large, a non-constant positive solution is generated, that is, stationary patterns emerge, depicting dispersal of species. Predators were observed to occupy habitats surrounding prey. However, super-predators were observed to alternate their habitats, from staying away from prey to invading prey habitat. In the investigation, strategies to determine ways in which the predator species could be saved from extinction and its population improved were devised, and these included isolation of the predator from the super-predator.
- Full Text:
- Date Issued: 2016
- Authors: Mbava, Willard
- Date: 2016
- Subjects: Predation (Biology) -- South Africa -- Kruger National Park Endangered species -- South Africa -- Kruger National Park
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11782 , vital:26968
- Description: The study involved the predator-prey interaction of three species namely the predator (Cheetah Acinonyx jubatus), the super-predator (Lion Panthera leo), and their common prey (Impala Aepyceros melampus). The study area is the Kruger National Park. The predator being an endangered species, faces a survival problem. It is frequently killed by the super-predator to reduce competition for prey. The super-predator also scares away the predator o_ its kills. The prey forms the main diet of the predator. The plight of the predator motivated the author to formulate disease and reaction-diffusion models for the species interactions. The purpose of the models were to predict and explain the effect of large competition from the super-predator on the predator population. Important parameters related to additional predator mortality due to presence of super-predator, the disease incidence rate and induced death rate formed the focal points of the analysis. The dynamics of a predator-prey model with disease in super-predator were investigated. The super-predator species is infected with bovine Tuberculosis. In the study, the disease is considered as biological control to allow the predator population to regain from low numbers. The results highlight that in the absence of additional mortality on the predator by the super-predator, the predator population survives extinction. Furthermore, at current levels of disease incidence, the super-predator population is wiped out by the disease. However, the super-predator population survives extinction if the disease incidence rate is low. Persistence of all populations is possible in the case of low disease incidence rate and no additional mortality imparted on the predator. Furthermore, a two-species subsystem, prey and predator, is considered as a special case to determine the effect of super-predator removal from the system, on the survival of the predator. This is treated as a contrasting case from the smaller parks. The results show that the predator population thrives well in the total absence of its main competitor, with its population rising to at least twice the initial value. A reaction-diffusion three-species predator-prey model was formulated and analysed. Stability of the temporal and the spatio-temporal systems, existence and non-existence of stationary steady state solutions were studied. Conditions for the emergence of stationary patterns were deduced. The results show that by choosing the diffusion coeffcient d2 > _D 2 suffciently large, a non-constant positive solution is generated, that is, stationary patterns emerge, depicting dispersal of species. Predators were observed to occupy habitats surrounding prey. However, super-predators were observed to alternate their habitats, from staying away from prey to invading prey habitat. In the investigation, strategies to determine ways in which the predator species could be saved from extinction and its population improved were devised, and these included isolation of the predator from the super-predator.
- Full Text:
- Date Issued: 2016
Benzoyl isothiocyanates derived ligands as potential HIV-1 protease inhibitors and their reactions with gold ions
- Authors: Odame, Felix
- Date: 2016
- Subjects: HIV (Viruses) -- Enzymes Enzyme inhibitors -- Research , Pharmaceutical chemistry Biochemistry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/33228 , vital:32585
- Description: The synthesis and evaluation of benzoyl isothiocyanate derivatives as potential HIV-1 protease inhibitors is presented. The ligands were first designed to fit the protease active site using Autodock 4.2. The design was based on the deNOVO method of drug design in which the active site coordinates from the crystal structure of protease bound to ritonavir was used. An attempt to access the scaffolds designed initially led to the formation of 2,2,4-trimethyl 2,3-dihydro-1H-1,5-benzodiazepin-5-ium isophthalate and 2-2-(3-methylphenyl-1Hbenzimidazole which could not be converted to the desired intermediate. A further attempt led to formation of amino acid and amino acid ester derivatives of benzoyl isothiocyanates which have been fully characterized and the reasons why the desired intermediates were not readily accessible explained. Scaffolds based on the benzoyl isothiocyanate derivatives of structurally diverse diamines were then screened. Sixty compounds have been synthesized and fully characterized using elemental analysis, spectroscopy, GC-MS and twenty-six crystal structures have been discussed. The DFT transition state studies of 11-phenyl- 1,8,10,12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,5,9,11-pentaene-13-thione (20), N-(1Hbenzimidazol-2-yl)benzamide (21), 3-(1,3-benzothiazol-2-yl)-1-(benzoyl)thiourea (23), and N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene] benzamide (39), have been carried out and their detailed density functional theory reaction mechanism have be computed. The Bernly algorithm was used in the determination of saddle points (transtions states), and the intrinsic reaction coordinates leading to the determination of intermediates were traced and optimized to a global minimum or in some cases a local minimum was obtained. The cell viability tests of diamine derivatives which was done by exposing white blood cells to the compounds (inhibitors) at 37 °C and a pH of 7.4 showed that 1-(4-bromobenzoyl)-3-[2- ({[(4-bromophenyl)formamido]methanethioyl}amino)phenyl]thiourea (46), 1-(3-chloro benzoyl)-3-[2-({[(3-chlorophenyl)formamido]methanethioyl}amino)phenyl]thiourea (48), 1- (3-bromobenzoyl)-3-[2-({[(3-bromophenyl)formamido]methanethioyl}amino)phenyl] thiourea (49) and 3-benzoyl-1-(4-{[(phenylformamido)methanethioyl]amino}butyl)thiourea (54), in that group of compounds were cytotoxic with EC50 values of 17.04 ± 9.75 μM, 69.20± 38.16 μM, 35.90 ± 20.55 μM and 68.37 ± 26.45 μM, respectively. 4-Bromo-N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene] benzamide (32), 4-methoxy-N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene]benzamide (33) and 3-chloro-N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene] benzamide (37) were also cytotoxic giving EC50 values of 45.47 ± 21.92, 45.09 ±13.79 and 74.94 ± 13.17 μM, respectively. 3-(1,3-Benzothiazol-2-yl)-1-(3-bromobenzoyl)thiourea (31) and 3-(1,3-benzothiazoyl-2-yl)-1-(4-nitrobenzoyl)thiourea (30) derivatives were also found to be cytotoxic with EC50 values of 1.207 ± 0.58 and 24.08 ±13.14 nM, respectively. 11-(4-Chlorophenyl-1,8,10, 12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,5,9,11-pentaene-13-thione (12), 11-(4-methoxyphenyl)-1,8,10,12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,9,1-pentaene-13-thione (14), and 11-phenyl-1,8,10,12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,5,9,11-pentaene-13-thione (20), were found to be cytotoxic giving EC50 values of 0.152 ± 0.051, 37.96 ± 21.87 and 5.28 ± 2.95 μM, respectively. In the enzyme inhibition studies compound 49 gave a percentage inhibition of 97.03 ± 10.61% at 100 μM, but the fact that it is cytoxic might make it less useful, whilst compounds 19 and 16 had a percentage inhibition of 59.57 ± 13.59% (4-nitro derivative) and 79.97 ± 11.97% (3-nitro derivative) respectively at 100 μM of inhibitor and 20 μM of enzyme (HIV-1 protease). The results suggests that the presence of the nitro group at position 3 (16) and 4 (19) leads to an increase in activity against HIV-1 protease.
- Full Text:
- Date Issued: 2016
- Authors: Odame, Felix
- Date: 2016
- Subjects: HIV (Viruses) -- Enzymes Enzyme inhibitors -- Research , Pharmaceutical chemistry Biochemistry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/33228 , vital:32585
- Description: The synthesis and evaluation of benzoyl isothiocyanate derivatives as potential HIV-1 protease inhibitors is presented. The ligands were first designed to fit the protease active site using Autodock 4.2. The design was based on the deNOVO method of drug design in which the active site coordinates from the crystal structure of protease bound to ritonavir was used. An attempt to access the scaffolds designed initially led to the formation of 2,2,4-trimethyl 2,3-dihydro-1H-1,5-benzodiazepin-5-ium isophthalate and 2-2-(3-methylphenyl-1Hbenzimidazole which could not be converted to the desired intermediate. A further attempt led to formation of amino acid and amino acid ester derivatives of benzoyl isothiocyanates which have been fully characterized and the reasons why the desired intermediates were not readily accessible explained. Scaffolds based on the benzoyl isothiocyanate derivatives of structurally diverse diamines were then screened. Sixty compounds have been synthesized and fully characterized using elemental analysis, spectroscopy, GC-MS and twenty-six crystal structures have been discussed. The DFT transition state studies of 11-phenyl- 1,8,10,12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,5,9,11-pentaene-13-thione (20), N-(1Hbenzimidazol-2-yl)benzamide (21), 3-(1,3-benzothiazol-2-yl)-1-(benzoyl)thiourea (23), and N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene] benzamide (39), have been carried out and their detailed density functional theory reaction mechanism have be computed. The Bernly algorithm was used in the determination of saddle points (transtions states), and the intrinsic reaction coordinates leading to the determination of intermediates were traced and optimized to a global minimum or in some cases a local minimum was obtained. The cell viability tests of diamine derivatives which was done by exposing white blood cells to the compounds (inhibitors) at 37 °C and a pH of 7.4 showed that 1-(4-bromobenzoyl)-3-[2- ({[(4-bromophenyl)formamido]methanethioyl}amino)phenyl]thiourea (46), 1-(3-chloro benzoyl)-3-[2-({[(3-chlorophenyl)formamido]methanethioyl}amino)phenyl]thiourea (48), 1- (3-bromobenzoyl)-3-[2-({[(3-bromophenyl)formamido]methanethioyl}amino)phenyl] thiourea (49) and 3-benzoyl-1-(4-{[(phenylformamido)methanethioyl]amino}butyl)thiourea (54), in that group of compounds were cytotoxic with EC50 values of 17.04 ± 9.75 μM, 69.20± 38.16 μM, 35.90 ± 20.55 μM and 68.37 ± 26.45 μM, respectively. 4-Bromo-N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene] benzamide (32), 4-methoxy-N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene]benzamide (33) and 3-chloro-N-[(9E)-8,10,17-triazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaen-9-ylidene] benzamide (37) were also cytotoxic giving EC50 values of 45.47 ± 21.92, 45.09 ±13.79 and 74.94 ± 13.17 μM, respectively. 3-(1,3-Benzothiazol-2-yl)-1-(3-bromobenzoyl)thiourea (31) and 3-(1,3-benzothiazoyl-2-yl)-1-(4-nitrobenzoyl)thiourea (30) derivatives were also found to be cytotoxic with EC50 values of 1.207 ± 0.58 and 24.08 ±13.14 nM, respectively. 11-(4-Chlorophenyl-1,8,10, 12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,5,9,11-pentaene-13-thione (12), 11-(4-methoxyphenyl)-1,8,10,12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,9,1-pentaene-13-thione (14), and 11-phenyl-1,8,10,12-tetraazatricyclo[7.4.0.02,7]trideca-2(7),3,5,9,11-pentaene-13-thione (20), were found to be cytotoxic giving EC50 values of 0.152 ± 0.051, 37.96 ± 21.87 and 5.28 ± 2.95 μM, respectively. In the enzyme inhibition studies compound 49 gave a percentage inhibition of 97.03 ± 10.61% at 100 μM, but the fact that it is cytoxic might make it less useful, whilst compounds 19 and 16 had a percentage inhibition of 59.57 ± 13.59% (4-nitro derivative) and 79.97 ± 11.97% (3-nitro derivative) respectively at 100 μM of inhibitor and 20 μM of enzyme (HIV-1 protease). The results suggests that the presence of the nitro group at position 3 (16) and 4 (19) leads to an increase in activity against HIV-1 protease.
- Full Text:
- Date Issued: 2016
Rhodes University Research Report 2016
- Rhodes University, Gillitt, Tarryn, Mantolo, Thumeka, Macgregor, Jill, Roberts, Jaine
- Authors: Rhodes University , Gillitt, Tarryn , Mantolo, Thumeka , Macgregor, Jill , Roberts, Jaine
- Date: 2016
- Language: English
- Type: Text
- Identifier: http://hdl.handle.net/10962/58288 , vital:27197
- Description: From Foreword by Dr Sizwe Mabizela: The results of the 2016 academic year were celebrated during a bumper graduation weekend in April 2017, in which a record 2 464 graduates were capped at 6 graduation ceremonies, 46% of whom were Postgraduates, 59% were women, and 21% were international students. A record number of 88 PhD degrees were awarded (up from 67 of 2016). We celebrated a new record of 29 PhD degrees for the Faculty of Humanities, up from the previous record of 19 achieved last year. The Faculty of Science produced 38 PhD graduates, the Faculty of Commerce 6, the Faculty of Education 13, and the Faculty of Pharmacy 2. All Faculties have done exceedingly well. Our warm congratulations go to all our Faculty Deans, Heads of Department and the academic and support staff who made this possible. , A publication of the Rhodes University Research Office, compiled and edited by: Tarryn Gillitt, Thumeka Mantolo, Jill Macgregor and Jaine Roberts.
- Full Text:
- Date Issued: 2016
- Authors: Rhodes University , Gillitt, Tarryn , Mantolo, Thumeka , Macgregor, Jill , Roberts, Jaine
- Date: 2016
- Language: English
- Type: Text
- Identifier: http://hdl.handle.net/10962/58288 , vital:27197
- Description: From Foreword by Dr Sizwe Mabizela: The results of the 2016 academic year were celebrated during a bumper graduation weekend in April 2017, in which a record 2 464 graduates were capped at 6 graduation ceremonies, 46% of whom were Postgraduates, 59% were women, and 21% were international students. A record number of 88 PhD degrees were awarded (up from 67 of 2016). We celebrated a new record of 29 PhD degrees for the Faculty of Humanities, up from the previous record of 19 achieved last year. The Faculty of Science produced 38 PhD graduates, the Faculty of Commerce 6, the Faculty of Education 13, and the Faculty of Pharmacy 2. All Faculties have done exceedingly well. Our warm congratulations go to all our Faculty Deans, Heads of Department and the academic and support staff who made this possible. , A publication of the Rhodes University Research Office, compiled and edited by: Tarryn Gillitt, Thumeka Mantolo, Jill Macgregor and Jaine Roberts.
- Full Text:
- Date Issued: 2016
Rhodes University Graduation Ceremony 2016
- Authors: Rhodes University
- Date: 2016
- Language: English
- Type: text
- Identifier: vital:8150 , http://hdl.handle.net/10962/d1021288
- Description: Rhodes University Graduation Ceremonies 2016 [at] 1820 Settlers National Monument Thursday, 31 March at 10.00 & 17:00 [and] Friday, 1 April at 10:00; 14:30 & 18:30 [and] Saturday, 2 April at 10:00
- Full Text:
- Date Issued: 2016
- Authors: Rhodes University
- Date: 2016
- Language: English
- Type: text
- Identifier: vital:8150 , http://hdl.handle.net/10962/d1021288
- Description: Rhodes University Graduation Ceremonies 2016 [at] 1820 Settlers National Monument Thursday, 31 March at 10.00 & 17:00 [and] Friday, 1 April at 10:00; 14:30 & 18:30 [and] Saturday, 2 April at 10:00
- Full Text:
- Date Issued: 2016