The photophysical and energy transfer behaviour of low symmetry phthalocyanine complexes conjugated to coreshell quantum dots
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243051 , vital:51111 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.07.016"
- Description: This work reports on the synthesis of new coreshell quantum dots (QDs)-low symmetry phthalocyanines conjugates. The energy transfer from QDs (donor) to phthalocyanines (acceptor) was investigated when the two are mixed together or chemically linked to each other. Ti monocarboxy phthalocyanine QDs-linked and Sn monocarboxy phthalocyanine QDs-linked gave the smallest centre-to-centre separation distance (r) corresponding to their higher Förster resonance energy transfer efficiencies which are estimated at 0.76 and 0.85 respectively. Higher energy transfer behaviour was achieved for all the covalently linked conjugates compared to their corresponding mixed counterparts. An improvement in triplet quantum yields and lifetimes was achieved for all the complexes in the presence of quantum dots, with the linked counterparts displaying excellent triplet state behaviour.
- Full Text:
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243051 , vital:51111 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.07.016"
- Description: This work reports on the synthesis of new coreshell quantum dots (QDs)-low symmetry phthalocyanines conjugates. The energy transfer from QDs (donor) to phthalocyanines (acceptor) was investigated when the two are mixed together or chemically linked to each other. Ti monocarboxy phthalocyanine QDs-linked and Sn monocarboxy phthalocyanine QDs-linked gave the smallest centre-to-centre separation distance (r) corresponding to their higher Förster resonance energy transfer efficiencies which are estimated at 0.76 and 0.85 respectively. Higher energy transfer behaviour was achieved for all the covalently linked conjugates compared to their corresponding mixed counterparts. An improvement in triplet quantum yields and lifetimes was achieved for all the complexes in the presence of quantum dots, with the linked counterparts displaying excellent triplet state behaviour.
- Full Text:
The praxis of responsible investment in South Africa: a holistic case study of Evolution One Fund
- Zaulochnaya Ya-Brouwer, Irina
- Authors: Zaulochnaya Ya-Brouwer, Irina
- Date: 2012
- Subjects: Social responsibility of business -- South Africa Investments -- Moral and ethical aspects -- South Africa Institutional investments -- Moral and ethical aspects -- South Africa Private equity funds -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:778 , http://hdl.handle.net/10962/d1003899
- Description: At the beginning of the 21st century the public interest in environmental and social sustainability, and corporate governance grew exponentially fuelled by recurring ecological and financial crises. The market demand for cleaner production and corporate transparency created opportunities for sustainability entrepreneurs in a variety of industries, including financial markets and investment management. An increasing number of financial institutions across the world now offer ethical or socially responsible products to meet the environmental, social and governance (ESG) aspirations of their clients. In the US, according to the Social Investment Forum (SIF), responsible investment (RI) assets reached US$ 2,29 trillion in 2007 (Mitchell, 2008). The European Sustainable Investment Forum (EuroSIF) estimated that total European SRI assets reached EUR 5 trillion in 2009 (Wheelan, 2010). In June 2011 the International Finance Corporation (IFC) reported that at the end of 2010 professional sustainable investment under management in South Africa approximately equalled US$ 122,6 billion (IFC, 2011:44). The statistics describing the rapid growth in the ESG-type investments are, however, complicated by the variety of names and definitions used to describe this emerging type of investment and a general market uncertainty about what constitutes the practice of RI. The purpose of this case study is to better understand responsible investment principles and practice as seen through the eyes of a South African private equity fund, which specializes in clean technology.
- Full Text:
- Authors: Zaulochnaya Ya-Brouwer, Irina
- Date: 2012
- Subjects: Social responsibility of business -- South Africa Investments -- Moral and ethical aspects -- South Africa Institutional investments -- Moral and ethical aspects -- South Africa Private equity funds -- South Africa
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:778 , http://hdl.handle.net/10962/d1003899
- Description: At the beginning of the 21st century the public interest in environmental and social sustainability, and corporate governance grew exponentially fuelled by recurring ecological and financial crises. The market demand for cleaner production and corporate transparency created opportunities for sustainability entrepreneurs in a variety of industries, including financial markets and investment management. An increasing number of financial institutions across the world now offer ethical or socially responsible products to meet the environmental, social and governance (ESG) aspirations of their clients. In the US, according to the Social Investment Forum (SIF), responsible investment (RI) assets reached US$ 2,29 trillion in 2007 (Mitchell, 2008). The European Sustainable Investment Forum (EuroSIF) estimated that total European SRI assets reached EUR 5 trillion in 2009 (Wheelan, 2010). In June 2011 the International Finance Corporation (IFC) reported that at the end of 2010 professional sustainable investment under management in South Africa approximately equalled US$ 122,6 billion (IFC, 2011:44). The statistics describing the rapid growth in the ESG-type investments are, however, complicated by the variety of names and definitions used to describe this emerging type of investment and a general market uncertainty about what constitutes the practice of RI. The purpose of this case study is to better understand responsible investment principles and practice as seen through the eyes of a South African private equity fund, which specializes in clean technology.
- Full Text:
The pump room
- Authors: Krueger, Anton
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/225764 , vital:49256 , xlink:href="https://doi.org/10.1080/10137548.2012.754084"
- Description: I like Allan Kolski Horwitz. He’s done great things for independent publishing in South Africa. Through his company, Botsotso, he’s probably responsible for publishing more poetry, prose and drama than any single person in the country today. The industriousness of his one-man operation has generously sponsored and nurtured thousands of pages of local literature over the course of many years. This is why it makes me so uncomfortable to say that I really don’t like this play. It gives me no pleasure to write a negative review, and especially not about books written by people I like. If I hadn’t already committed myself to writing this review, I would have avoided it. Nevertheless, I had, so I won’t.
- Full Text:
- Authors: Krueger, Anton
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/225764 , vital:49256 , xlink:href="https://doi.org/10.1080/10137548.2012.754084"
- Description: I like Allan Kolski Horwitz. He’s done great things for independent publishing in South Africa. Through his company, Botsotso, he’s probably responsible for publishing more poetry, prose and drama than any single person in the country today. The industriousness of his one-man operation has generously sponsored and nurtured thousands of pages of local literature over the course of many years. This is why it makes me so uncomfortable to say that I really don’t like this play. It gives me no pleasure to write a negative review, and especially not about books written by people I like. If I hadn’t already committed myself to writing this review, I would have avoided it. Nevertheless, I had, so I won’t.
- Full Text:
The recognition of unenumerated rights in South Africa
- Krüger, Rósaan, Govindjee, Avinash
- Authors: Krüger, Rósaan , Govindjee, Avinash
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/71093 , vital:29783 , https://hdl.handle.net/10520/EJC153177
- Description: In 1997 a South African man married a woman who, at the time of the conclusion of their marriage, was a national of a foreign country. The couple decided to set up home and start a family in South Africa. They were advised that the granting of a permanent residence permit to the wife would only be considered upon payment of a hefty application fee, and that she had to apply for the permit from outside South Africa. The couple was of the view that the high cost of the application coupled with their temporary separation at the time of the lodging of the application amounted to an unjustifiable limitation of their right to family life. One of the obstacles faced by the couple was the silence of the South Africa Constitution on the right to family life.
- Full Text: false
- Authors: Krüger, Rósaan , Govindjee, Avinash
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/71093 , vital:29783 , https://hdl.handle.net/10520/EJC153177
- Description: In 1997 a South African man married a woman who, at the time of the conclusion of their marriage, was a national of a foreign country. The couple decided to set up home and start a family in South Africa. They were advised that the granting of a permanent residence permit to the wife would only be considered upon payment of a hefty application fee, and that she had to apply for the permit from outside South Africa. The couple was of the view that the high cost of the application coupled with their temporary separation at the time of the lodging of the application amounted to an unjustifiable limitation of their right to family life. One of the obstacles faced by the couple was the silence of the South Africa Constitution on the right to family life.
- Full Text: false
The role of culture in enabling or constraining the use of technology in higher education teaching and learning: the Commerce Curriculum Project
- Mostert, Markus, Snowball, Jeanette D, Boughey, Chrissie
- Authors: Mostert, Markus , Snowball, Jeanette D , Boughey, Chrissie
- Date: 2012
- Language: English
- Type: conference paper , text
- Identifier: http://hdl.handle.net/10962/61073 , vital:27945
- Description: This paper draws on a project located in one faculty at a South African university which aimed to use Information and Communication Technologies (ICTs) to enhance teaching and learning. More specifically, the paper uses Archer’s (1995, 1996, 2000, 1998) ‘analytical dualism’ and ‘morphogenesis’ to explore the way individuals involved in the project were able to exercise agency in departments which were relatively hostile to the goals they were aiming to pursue despite the wider cultural domain encompassing many ideas which construct the use of ICTs as significant in promoting student learning. The paper thus contributes to the culture/agency subtheme of the HECU6 conference. The paper begins by providing some background to the project before moving on to an exploration of the way Archer’s theoretical work was used to analyse data collected by project leaders.
- Full Text:
- Authors: Mostert, Markus , Snowball, Jeanette D , Boughey, Chrissie
- Date: 2012
- Language: English
- Type: conference paper , text
- Identifier: http://hdl.handle.net/10962/61073 , vital:27945
- Description: This paper draws on a project located in one faculty at a South African university which aimed to use Information and Communication Technologies (ICTs) to enhance teaching and learning. More specifically, the paper uses Archer’s (1995, 1996, 2000, 1998) ‘analytical dualism’ and ‘morphogenesis’ to explore the way individuals involved in the project were able to exercise agency in departments which were relatively hostile to the goals they were aiming to pursue despite the wider cultural domain encompassing many ideas which construct the use of ICTs as significant in promoting student learning. The paper thus contributes to the culture/agency subtheme of the HECU6 conference. The paper begins by providing some background to the project before moving on to an exploration of the way Archer’s theoretical work was used to analyse data collected by project leaders.
- Full Text:
The role of Hsp90/Hsp70 organising protein (Hop) in the Proliferation, Survival and Migration of Breast Cancer Cells.
- Authors: Willmer, Tarryn
- Date: 2012
- Subjects: Cancer -- Treatment , Heat shock proteins , Cancer cells , Breast -- Cancer
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4130 , http://hdl.handle.net/10962/d1015720
- Description: Hop (the Hsp90/Hsp70 organising protein) is a co-chaperone that acts as an adapter between the major molecular chaperones Hsp90 and Hsp70 during the cellular assembly of the Hsp90 complex. The Hsp90 complex regulates the stability and conformational maturation of a range of important cellular proteins, many of which are deregulated in cancer. In this study, we hypothesised that Hop knockdown inhibits proliferation and migration of cancer cells. We characterised the expression of Hop in cell models of different cancerous status, and provided evidence that Hop was upregulated in tumour cells compared to normal cell counterparts. Using an RNA interference approach, a 60-90% knockdown of Hop was achieved for up to 144 hours in the MDA-MB-231 and Hs578T breast cancer cell lines. Hop knockdown resulted in downregulation of the Hsp90 client proteins, Akt and Stat3, as well as a change in the expression of other Hsp90 co-chaperones, p23, Cdc37 and Aha1, while no change in the levels of Hsp90 or Hsp70 was observed. Silencing of Hop impaired cell proliferation in Hs578T cells but an increase in proliferation in MDA-MB-231, suggesting that the role of Hop in cancer cell proliferation was dependent on type of cancer cell. Hop knockdown in Hs578T and MDA-MB- 231 cells did not lead to any significant changes in the half maximal inhibitory concentrations (IC50) of selected small molecule inhibitors (paclitaxel, geldanamycin and novobiocin) in these cell lines after 72 hours. Hop knockdown cells were however, more sensitive than control cells to the Hsp90 inhibitors geldanamycin and novobiocin at earlier time points and in the presence of the drug transporter inhibitor, verapamil. Hop knockdown caused a decrease in cell migration as measured by the wound healing assay in both Hs578T and MDA-MB-231 cells. Hop was present in purified pseudopodia fractions of migrating cells, and immunofluorescence analysis showed that Hop colocalised with actin at the leading edges of pseudopodia, points of adhesion and at intercellular junctions of cells that have been stimulated to migrate with the chemokine stromal derived factor-1. Hop was able to bind to actin in vitro using actin cosedimentation assays, and silencing of Hop dramatically reduced the capacity of Hs578T cells to form pseudopodia. These results establish a correlation between Hop and actin dynamics, pseudopodia formation and migration in the context of Hop silencing, and collectively suggest that Hop plays a role in cancer cell migration. This study presents experimental evidence for a promising alternative to targeting Hsp90 and Hsp70 chaperones, a novel drug target in cancer therapy.
- Full Text:
- Authors: Willmer, Tarryn
- Date: 2012
- Subjects: Cancer -- Treatment , Heat shock proteins , Cancer cells , Breast -- Cancer
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4130 , http://hdl.handle.net/10962/d1015720
- Description: Hop (the Hsp90/Hsp70 organising protein) is a co-chaperone that acts as an adapter between the major molecular chaperones Hsp90 and Hsp70 during the cellular assembly of the Hsp90 complex. The Hsp90 complex regulates the stability and conformational maturation of a range of important cellular proteins, many of which are deregulated in cancer. In this study, we hypothesised that Hop knockdown inhibits proliferation and migration of cancer cells. We characterised the expression of Hop in cell models of different cancerous status, and provided evidence that Hop was upregulated in tumour cells compared to normal cell counterparts. Using an RNA interference approach, a 60-90% knockdown of Hop was achieved for up to 144 hours in the MDA-MB-231 and Hs578T breast cancer cell lines. Hop knockdown resulted in downregulation of the Hsp90 client proteins, Akt and Stat3, as well as a change in the expression of other Hsp90 co-chaperones, p23, Cdc37 and Aha1, while no change in the levels of Hsp90 or Hsp70 was observed. Silencing of Hop impaired cell proliferation in Hs578T cells but an increase in proliferation in MDA-MB-231, suggesting that the role of Hop in cancer cell proliferation was dependent on type of cancer cell. Hop knockdown in Hs578T and MDA-MB- 231 cells did not lead to any significant changes in the half maximal inhibitory concentrations (IC50) of selected small molecule inhibitors (paclitaxel, geldanamycin and novobiocin) in these cell lines after 72 hours. Hop knockdown cells were however, more sensitive than control cells to the Hsp90 inhibitors geldanamycin and novobiocin at earlier time points and in the presence of the drug transporter inhibitor, verapamil. Hop knockdown caused a decrease in cell migration as measured by the wound healing assay in both Hs578T and MDA-MB-231 cells. Hop was present in purified pseudopodia fractions of migrating cells, and immunofluorescence analysis showed that Hop colocalised with actin at the leading edges of pseudopodia, points of adhesion and at intercellular junctions of cells that have been stimulated to migrate with the chemokine stromal derived factor-1. Hop was able to bind to actin in vitro using actin cosedimentation assays, and silencing of Hop dramatically reduced the capacity of Hs578T cells to form pseudopodia. These results establish a correlation between Hop and actin dynamics, pseudopodia formation and migration in the context of Hop silencing, and collectively suggest that Hop plays a role in cancer cell migration. This study presents experimental evidence for a promising alternative to targeting Hsp90 and Hsp70 chaperones, a novel drug target in cancer therapy.
- Full Text:
The role of leadership in implementing service delivery initiatives: a case study of Buffalo City Municipality
- Authors: Mthembu, Bhekisisa Jacob
- Date: 2012
- Subjects: Local government -- South Africa -- Buffalo City Municipal services -- Management -- South Africa -- Buffalo City Public administration -- South Africa -- Buffalo City Political leadership -- South Africa -- Buffalo City Buffalo City (South Africa) -- Officials and employees Municipal officials and employees -- South Africa -- Buffalo City Municipal services -- South Africa -- Buffalo -- Citizen participation
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:781 , http://hdl.handle.net/10962/d1003902
- Description: In terms of the South African Government Structure, Local Government is entrusted with the service delivery mandate. Furthermore, Local Government, being the closest sphere of government to the people, is expected to enhance service delivery to the communities within its jurisdiction. Local Government has for the past four years, undergone numerous transformation processes, ranging from Local Authorities, to Transitional Local Councils and to Municipalities. Having mentioned that, Buffalo City Metropolitan Municipality, in particular, has recently acquired metropolitan status, which requires another transformation protocol. At the same time this automatically raises the bar on the service delivery expectations by the communities. In general, Local Government has been extensively supported by the National and Provincial Governments to deliver superior services to communities. This has happened through numerous pieces of legislations such as the Municipal Structures Act 117 of 1998, the Municipal Systems Act 32 of 2000, the Municipal Finance Management Act 56 of 2003 and the Constitution of the Republic of South Africa, act 108 of 1996. In 1997, the South African Government introduced a White Paper on the Transformation of the Public Service. This was to re-emphasis on the performance enhancing role of both the political and administrative leadership in the implementation of service delivery mandates. The need was identified that communities require an assurance that their needs are taken care of by the leadership of the municipalities. It is therefore the role of leadership to ensure effective implementation of service delivery initiatives and to promote a culture of performance among the administrative officials of the municipality. The aim of this study is to critically investigate the role of leadership: A case study of Buffalo City Metropolitan Municipality (BCMM), with the view that BCMM is considered one of the high capacity municipalities within the Eastern Cape Province. During the literature review, it became evident that different people and scholars, dating back in the early 90’s, view leadership in different forms. In sourcing the information for this research, structured interviews were conducted with five Directors, five Executive Mayoral Councillors and five Ward Councillors. The interviews were an extensive consultation process which resulted in over 30 hours of engagement with research participants, with an average of 2 hours per structured interview. A four week period was allocated and effectively utilised for this exercise. The research provides recommendations for further research on other related components of the subject such as the intended role as compared to the current role fulfilled by both administrative and political leadership, and suggested solutions to the current problems in Municipalities, in order to ensure their sustainability within Local Government. The research findings identified the need for the leadership to take the leading role in service delivery initiatives in order to address the service delivery challenges in local government. Political leadership need to enhance the public participation process to ensure the community is on board regarding the progress of their respective projects and planning processes.
- Full Text:
- Authors: Mthembu, Bhekisisa Jacob
- Date: 2012
- Subjects: Local government -- South Africa -- Buffalo City Municipal services -- Management -- South Africa -- Buffalo City Public administration -- South Africa -- Buffalo City Political leadership -- South Africa -- Buffalo City Buffalo City (South Africa) -- Officials and employees Municipal officials and employees -- South Africa -- Buffalo City Municipal services -- South Africa -- Buffalo -- Citizen participation
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:781 , http://hdl.handle.net/10962/d1003902
- Description: In terms of the South African Government Structure, Local Government is entrusted with the service delivery mandate. Furthermore, Local Government, being the closest sphere of government to the people, is expected to enhance service delivery to the communities within its jurisdiction. Local Government has for the past four years, undergone numerous transformation processes, ranging from Local Authorities, to Transitional Local Councils and to Municipalities. Having mentioned that, Buffalo City Metropolitan Municipality, in particular, has recently acquired metropolitan status, which requires another transformation protocol. At the same time this automatically raises the bar on the service delivery expectations by the communities. In general, Local Government has been extensively supported by the National and Provincial Governments to deliver superior services to communities. This has happened through numerous pieces of legislations such as the Municipal Structures Act 117 of 1998, the Municipal Systems Act 32 of 2000, the Municipal Finance Management Act 56 of 2003 and the Constitution of the Republic of South Africa, act 108 of 1996. In 1997, the South African Government introduced a White Paper on the Transformation of the Public Service. This was to re-emphasis on the performance enhancing role of both the political and administrative leadership in the implementation of service delivery mandates. The need was identified that communities require an assurance that their needs are taken care of by the leadership of the municipalities. It is therefore the role of leadership to ensure effective implementation of service delivery initiatives and to promote a culture of performance among the administrative officials of the municipality. The aim of this study is to critically investigate the role of leadership: A case study of Buffalo City Metropolitan Municipality (BCMM), with the view that BCMM is considered one of the high capacity municipalities within the Eastern Cape Province. During the literature review, it became evident that different people and scholars, dating back in the early 90’s, view leadership in different forms. In sourcing the information for this research, structured interviews were conducted with five Directors, five Executive Mayoral Councillors and five Ward Councillors. The interviews were an extensive consultation process which resulted in over 30 hours of engagement with research participants, with an average of 2 hours per structured interview. A four week period was allocated and effectively utilised for this exercise. The research provides recommendations for further research on other related components of the subject such as the intended role as compared to the current role fulfilled by both administrative and political leadership, and suggested solutions to the current problems in Municipalities, in order to ensure their sustainability within Local Government. The research findings identified the need for the leadership to take the leading role in service delivery initiatives in order to address the service delivery challenges in local government. Political leadership need to enhance the public participation process to ensure the community is on board regarding the progress of their respective projects and planning processes.
- Full Text:
The saga of South African POWs in Angola, 1975-82
- Authors: Baines, Gary F
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69882 , vital:29592 , http://dx.doi.org/10.5787/40-2-999
- Description: This article narrates the story of nine soldiers captured during and shortly after Operation Savannah, the codename for the South African Defence Force invasion of Angola in 1975–6. Eight of these soldiers were captured in Angola in three separate incidents by Angolan and/or Cuban forces, whereas the last was abducted from northern Namibia by SWAPO (the South West Africa Peoples’ Organisation). The article then provides a chronological account of the sequels to this story that interweaves a number of threads: first, the account relates the South African government’s attempts to suppress press coverage of these stories for fear of the political ‘fall-out’ that the matter might cause amongst the white electorate and in case it jeopardised secret negotiations to secure the release of the prisoners; and second, it uncovers the role played by intermediaries, especially the International Committee of the Red Cross (ICRC), in the sensitive and fraught negotiation process. It will be shown that the South African authorities adopted divergent approaches when dealing with SWAPO and the Angolans/Cubans to secure the release of prisoners of war (POWs). This is because the South African authorities regarded the former as involved in an internal insurrection whereas the latter were members of the military forces of sovereign states. Accordingly, they paid lip service to the Geneva Conventions in the case of Angolan and Cuban POWs but treated captured SWAPO cadres as ‘terrorists’ or ‘criminals’.
- Full Text:
- Authors: Baines, Gary F
- Date: 2012
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69882 , vital:29592 , http://dx.doi.org/10.5787/40-2-999
- Description: This article narrates the story of nine soldiers captured during and shortly after Operation Savannah, the codename for the South African Defence Force invasion of Angola in 1975–6. Eight of these soldiers were captured in Angola in three separate incidents by Angolan and/or Cuban forces, whereas the last was abducted from northern Namibia by SWAPO (the South West Africa Peoples’ Organisation). The article then provides a chronological account of the sequels to this story that interweaves a number of threads: first, the account relates the South African government’s attempts to suppress press coverage of these stories for fear of the political ‘fall-out’ that the matter might cause amongst the white electorate and in case it jeopardised secret negotiations to secure the release of the prisoners; and second, it uncovers the role played by intermediaries, especially the International Committee of the Red Cross (ICRC), in the sensitive and fraught negotiation process. It will be shown that the South African authorities adopted divergent approaches when dealing with SWAPO and the Angolans/Cubans to secure the release of prisoners of war (POWs). This is because the South African authorities regarded the former as involved in an internal insurrection whereas the latter were members of the military forces of sovereign states. Accordingly, they paid lip service to the Geneva Conventions in the case of Angolan and Cuban POWs but treated captured SWAPO cadres as ‘terrorists’ or ‘criminals’.
- Full Text:
The solo piano music of Einojuhani Rautavaara
- Authors: Matambo, Lotta Eleonoora
- Date: 2012
- Subjects: Rautavaara, Einojuhani, 1928 -- Piano music -- Criticism and interpretation Piano music -- History and criticism
- Language: English
- Type: Thesis , Masters , MMus
- Identifier: vital:2646 , http://hdl.handle.net/10962/d1002311
- Description: Einojuhani Rautavaara's oeuvre is characterised by four distinctive creative periods, each demonstrating a remarkable variety of compositional idioms and styles. His application of multifaceted elements, often within a single work leading to notions of postmodernism, is derived from multifarious sources, such as (Finnish) folklore, Orthodox mysticism and a wide variety of standard twentieth century compositional techniques. Furthermore, Rautavaara regularly quotes from his own material, thus creating elements of auto-allusions within his oeuvre; a predisposition which forms an essential part of his compositional aesthetic. Analyses of eight piano works (1952-2007) provide a cross-section of Rautavaara's output which, together with a consideration of biographical factors and analytical focus on the intertextual elements of his writing, offers a rationale for determining the development of his musical identity. The analyses conclude that intertextual elements, which appear through a diverse array of expressive modes (such as mysticism, nationalism and constructivism) are an essential part of Rautavaara's eclectic compositional style and contribute to an understanding of the on-going development of his musical identity.
- Full Text:
- Authors: Matambo, Lotta Eleonoora
- Date: 2012
- Subjects: Rautavaara, Einojuhani, 1928 -- Piano music -- Criticism and interpretation Piano music -- History and criticism
- Language: English
- Type: Thesis , Masters , MMus
- Identifier: vital:2646 , http://hdl.handle.net/10962/d1002311
- Description: Einojuhani Rautavaara's oeuvre is characterised by four distinctive creative periods, each demonstrating a remarkable variety of compositional idioms and styles. His application of multifaceted elements, often within a single work leading to notions of postmodernism, is derived from multifarious sources, such as (Finnish) folklore, Orthodox mysticism and a wide variety of standard twentieth century compositional techniques. Furthermore, Rautavaara regularly quotes from his own material, thus creating elements of auto-allusions within his oeuvre; a predisposition which forms an essential part of his compositional aesthetic. Analyses of eight piano works (1952-2007) provide a cross-section of Rautavaara's output which, together with a consideration of biographical factors and analytical focus on the intertextual elements of his writing, offers a rationale for determining the development of his musical identity. The analyses conclude that intertextual elements, which appear through a diverse array of expressive modes (such as mysticism, nationalism and constructivism) are an essential part of Rautavaara's eclectic compositional style and contribute to an understanding of the on-going development of his musical identity.
- Full Text:
The strategic alignment maturity of business and information technology at Volkswagen South Africa
- Authors: Naidoo, Lavendra
- Date: 2012
- Subjects: Industrial management -- South Africa Industrial management Business enterprises -- Information technology -- Management
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:789 , http://hdl.handle.net/10962/d1003910
- Description: During the past three decades Information Technology (IT) has been constantly evolving and has emerged into a significant component and enabler of most organisations strategy, to the point that modern day organisations are intrinsically dependent on IT (Peppard and Ward, 2004). Henderson and Venkatraman (1993) advocate that for an organisation to be successful in a dynamic and competitive business environment it is imperative that there is an effective and efficient IT strategy that enables the business strategy and processes. Volkswagen South Africa (VWSA)in 2007 launched its corporate strategy, 1:10:100 – 2010 At the end of this stated period 2010, VWSA achieved several of its objectives, namely surpassing its competitors in passenger vehicle sales volume, improving its customer satisfaction, achieving a higher level of local parts content per unit, developing its people and improving its infrastructure and processes.
- Full Text:
- Authors: Naidoo, Lavendra
- Date: 2012
- Subjects: Industrial management -- South Africa Industrial management Business enterprises -- Information technology -- Management
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:789 , http://hdl.handle.net/10962/d1003910
- Description: During the past three decades Information Technology (IT) has been constantly evolving and has emerged into a significant component and enabler of most organisations strategy, to the point that modern day organisations are intrinsically dependent on IT (Peppard and Ward, 2004). Henderson and Venkatraman (1993) advocate that for an organisation to be successful in a dynamic and competitive business environment it is imperative that there is an effective and efficient IT strategy that enables the business strategy and processes. Volkswagen South Africa (VWSA)in 2007 launched its corporate strategy, 1:10:100 – 2010 At the end of this stated period 2010, VWSA achieved several of its objectives, namely surpassing its competitors in passenger vehicle sales volume, improving its customer satisfaction, achieving a higher level of local parts content per unit, developing its people and improving its infrastructure and processes.
- Full Text:
The structural arrangements in local government and their role in promoting community participation in basic service delivery: a case study of Emalahleni and Intsika Yethu local municipalities in the Chris Hani District Municipality area
- Authors: Nqwemeshe, Nomvuyo
- Date: 2012
- Subjects: Local government -- South Africa -- Eastern Cape , Municipal services -- South Africa -- Eastern Cape -- Citizen participation , Water utilities -- South Africa -- Eastern Cape -- Citizen participation , Water-supply -- South Africa -- Eastern Cape -- Citizen participation , Community development -- South Africa -- Eastern Cape , Economic development projects -- Evaluation -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:3315 , http://hdl.handle.net/10962/d1003103
- Description: This study analyses the effectiveness of community participation in service delivery. The area of study, the Chris Ham District Municipality (CHDM), is a Water Services Authority, responsible for ensuring access to water services (water and sanitation) by all communities within its jurisdiction. There are eight local municipalities within the CHDM. The objective of this study is to determine whether systems are in place in local government to promote participation by communities in service delivery projects and whether these systems are being utilised efficiently by the role-players concerned. The role-players in this research are people who are involved in community development programmes of the municipality (municipal staff in the relevant departments of the municipalities under study, the social facilitators, civil society organisations, ward committees, ward councillors, traditional authorities as well as the representatives of communities (Project Steering Committees) who are beneficiaries of the projects under study). The projects that are under study were selected from a readily available list of CHDM capital projects that appear in the 2003/2004 financial year funding plan and are running. The findings of the study at both levels (local and district) show that the municipal environment is not conducive to promoting community participation. This is linked to factors such as the structural arrangements, whereby the offices relevant for promoting community participation are not fully occupied, which provided evidence that community participation is not prioritised. There is lack of coordination of programmes within the local government spheres as well within departments of the DM and strategies for community participation have been found to be non-effective. At project level lack of community participation is linked to the utilisation of ward committees as the only mechanism for community participation regardless of its un-equal and party biased representation. This study therefore concludes that although the systems to promote community participation are in place, they are not effective.
- Full Text:
- Authors: Nqwemeshe, Nomvuyo
- Date: 2012
- Subjects: Local government -- South Africa -- Eastern Cape , Municipal services -- South Africa -- Eastern Cape -- Citizen participation , Water utilities -- South Africa -- Eastern Cape -- Citizen participation , Water-supply -- South Africa -- Eastern Cape -- Citizen participation , Community development -- South Africa -- Eastern Cape , Economic development projects -- Evaluation -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:3315 , http://hdl.handle.net/10962/d1003103
- Description: This study analyses the effectiveness of community participation in service delivery. The area of study, the Chris Ham District Municipality (CHDM), is a Water Services Authority, responsible for ensuring access to water services (water and sanitation) by all communities within its jurisdiction. There are eight local municipalities within the CHDM. The objective of this study is to determine whether systems are in place in local government to promote participation by communities in service delivery projects and whether these systems are being utilised efficiently by the role-players concerned. The role-players in this research are people who are involved in community development programmes of the municipality (municipal staff in the relevant departments of the municipalities under study, the social facilitators, civil society organisations, ward committees, ward councillors, traditional authorities as well as the representatives of communities (Project Steering Committees) who are beneficiaries of the projects under study). The projects that are under study were selected from a readily available list of CHDM capital projects that appear in the 2003/2004 financial year funding plan and are running. The findings of the study at both levels (local and district) show that the municipal environment is not conducive to promoting community participation. This is linked to factors such as the structural arrangements, whereby the offices relevant for promoting community participation are not fully occupied, which provided evidence that community participation is not prioritised. There is lack of coordination of programmes within the local government spheres as well within departments of the DM and strategies for community participation have been found to be non-effective. At project level lack of community participation is linked to the utilisation of ward committees as the only mechanism for community participation regardless of its un-equal and party biased representation. This study therefore concludes that although the systems to promote community participation are in place, they are not effective.
- Full Text:
The symmetry group of a model of hyperbolic plane geometry and some associated invariant optimal control problems
- Authors: Henninger, Helen Clare
- Date: 2012
- Subjects: Geometry , Symmetry groups , Symmetry (Mathematics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5432 , http://hdl.handle.net/10962/d1018232
- Description: In this thesis we study left-invariant control offine systems on the symmetry group of a. model of hyperbolic plane geometry, the matrix Lie group SO(1, 2)₀. We determine that there are 10 distinct classes of such control systems and for typical elements of two of these classes we provide solutions of the left-invariant optimal wntrol problem with quauratic costs. Under the identification of the Lie allgebra .so(l, 2) with Minkowski spacetime R¹̕'², we construct a controllabilility criterion for all left-invariant control affine systems on 50(1. 2)₀ which in the inhomogeneous case depends only on the presence or absence of an element in the image of the system's trace in R¹̕ ²which is identifiable using the inner product. For the solutions of both the optimal control problems, we provide explicit expressions in terms of Jacobi elliptic functions for the solutions of the reduced extremal equations and determine the nonlinear stability of the equilibrium points.
- Full Text:
- Authors: Henninger, Helen Clare
- Date: 2012
- Subjects: Geometry , Symmetry groups , Symmetry (Mathematics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5432 , http://hdl.handle.net/10962/d1018232
- Description: In this thesis we study left-invariant control offine systems on the symmetry group of a. model of hyperbolic plane geometry, the matrix Lie group SO(1, 2)₀. We determine that there are 10 distinct classes of such control systems and for typical elements of two of these classes we provide solutions of the left-invariant optimal wntrol problem with quauratic costs. Under the identification of the Lie allgebra .so(l, 2) with Minkowski spacetime R¹̕'², we construct a controllabilility criterion for all left-invariant control affine systems on 50(1. 2)₀ which in the inhomogeneous case depends only on the presence or absence of an element in the image of the system's trace in R¹̕ ²which is identifiable using the inner product. For the solutions of both the optimal control problems, we provide explicit expressions in terms of Jacobi elliptic functions for the solutions of the reduced extremal equations and determine the nonlinear stability of the equilibrium points.
- Full Text:
The syntheses and photophysical properties of 4, 4′-isopropylidendioxydiphenyl substituted ball-type dinuclear Mg (II) and Zn (II) phthalocyanines
- Canlıca, Mevlüde, Nyokong, Tebello
- Authors: Canlıca, Mevlüde , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243554 , vital:51163 , xlink:href="https://doi.org/10.1016/j.poly.2011.10.024"
- Description: The syntheses of ball-type dinuclear Zn(II) and Mg(II) phthalocyanines containing four 4,4′-isopropylidendioxydiphenyl substituents at the peripheral and non-peripheral positions are presented. The structures of the synthesized compounds were characterized using elemental analyses, and UV–Vis, FT-IR, 1H NMR and mass spectroscopies. The ΦF values were 0.14, 0.11, 0.22, 0.15 and ΦT values were 0.84, 0.88, 0.62, 0.74, for 6–9, respectively. The largest triplet yields were observed for the non-peripherally substituted complexes 6 and 7, showing that non-peripheral substitution favors increased population of the triplet state. All complexes showed reasonably long triplet lifetimes with τT 510, 310, 910 and 350 μs in DMSO, respectively.
- Full Text:
- Authors: Canlıca, Mevlüde , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243554 , vital:51163 , xlink:href="https://doi.org/10.1016/j.poly.2011.10.024"
- Description: The syntheses of ball-type dinuclear Zn(II) and Mg(II) phthalocyanines containing four 4,4′-isopropylidendioxydiphenyl substituents at the peripheral and non-peripheral positions are presented. The structures of the synthesized compounds were characterized using elemental analyses, and UV–Vis, FT-IR, 1H NMR and mass spectroscopies. The ΦF values were 0.14, 0.11, 0.22, 0.15 and ΦT values were 0.84, 0.88, 0.62, 0.74, for 6–9, respectively. The largest triplet yields were observed for the non-peripherally substituted complexes 6 and 7, showing that non-peripheral substitution favors increased population of the triplet state. All complexes showed reasonably long triplet lifetimes with τT 510, 310, 910 and 350 μs in DMSO, respectively.
- Full Text:
The synthesis and breast cancer inhibitory activity of cinnamic acid analogues based on the halogenated monoterpene pharmacophore
- Authors: Chiwakata, Maynard Tendai
- Date: 2012
- Subjects: Halocarbons , Cancer -- Treatment , Breast -- Cancer -- Treatment
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3866 , http://hdl.handle.net/10962/d1016129
- Description: Breast cancer is one of the leading causes of death, with mortality rate estimates of 465 000 deaths per annum. It is estimated that 1.3 million women are diagnosed with the disease each year especially in the developing countries. Current chemotherapy relies on the use of high doses of non-specific toxic agents that possess adverse side effects and compromise patient’s compliance and adherence to treatment. Paclitaxel, one of the common drugs used in breast cancer chemotherapy results in sensory and motor neuropathy, whilst hormonal therapy e.g. Herceptin causes severe cardiovascular, gastrointestinal and cutaneous side effects. There has been a demand in developing newer cancer agents that demonstrate selective cytoxicity with minimal effect on normal body tissue. Numerous studies have shown that marine organisms produce a wide range of halogenated compounds that possess cytotoxic properties, and hence can be a source of new drug hits or leads for cancer therapy. Halomon, a polyhalogenated monoterpene from Portieria hornemannii, displayed interesting activity against brain, renal and lung cancer tumours with selective/differential cytotoxicity. This inspired us to focus our project on halogenated monoterpenes isolated from the same Rhodophyta class as P. hornemannii but with particular attention to Plocamium species. Several metabolites have been isolated from P. cornutum, P. corallorhiza and P. suhrii that possess interesting cytotoxicities against a breast cancer cell line (MCF7) and an oesophageal cancer line (WHCO1). The aim of the project was therefore centred at isolating target compounds for preliminary structure-activity studies against a breast cancer cell line, and use this information to synthesize a series of analogues that are more stable than the natural products and yet as active using a fragment-based type approach to map out pharmacophoric elements. Five metabolites were isolated from P. cornutum and five from P. corallorhiza. Cell-based assays were conducted using an MTT assay kit against MCF7 and MDA-MB-231 breast cancer cell lines and (1E,3E,5S,6R)-1,5,6-trichloro-2-(dichloromethyl)-6-methylocta-1,3,7-triene, isolated from P. cornutum was the most active with IC50 values of 3.0 μM and 6.15 μM respectively. Introduction of a terminal aromatic ring to enhance stability, together with varying substituents (H, CH3, CF3, Br, CN, CHO, CHCl2) on position 7 of the molecule, gave rise to a series of cinnamate ester derivatives inspired by (1E,3E,5S,6R)-1,5,6-trichloro-2-(dichloromethyl)-6-methylocta-1,3,7-triene. The analogues were synthesized from their benzaldehyde precursors via Aldol condensation, esterification and Wittig reactions. Their carboxylic acid counterparts were synthesized by hydrolysis of the parent esters in an attempt to promote water solubilities of the analogues. Biological activity assays were then conducted with the cinnamate analogues against the MDA-MB-231 breast cancer cell line using an MTT assay kit. Ester derivatives with -CHO and -CHCl2 functionalities had IC50 values of 43.45 μM and 100.01 μM respectively whilst the other ester derivatives were inactive. It was concluded that either an aldehyde (-CHO) or gem-dichlorides (-CHCl2) is specifically required for cytotoxic activity to be observed. None of the carboxylic acids were active which could have been due to failure of the compounds to enter the breast cancer cells and reach the target site because of their polar nature. Compounds with -CHO and -CHCl2 functionalities were therefore selected for future SARs studies.
- Full Text:
- Authors: Chiwakata, Maynard Tendai
- Date: 2012
- Subjects: Halocarbons , Cancer -- Treatment , Breast -- Cancer -- Treatment
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3866 , http://hdl.handle.net/10962/d1016129
- Description: Breast cancer is one of the leading causes of death, with mortality rate estimates of 465 000 deaths per annum. It is estimated that 1.3 million women are diagnosed with the disease each year especially in the developing countries. Current chemotherapy relies on the use of high doses of non-specific toxic agents that possess adverse side effects and compromise patient’s compliance and adherence to treatment. Paclitaxel, one of the common drugs used in breast cancer chemotherapy results in sensory and motor neuropathy, whilst hormonal therapy e.g. Herceptin causes severe cardiovascular, gastrointestinal and cutaneous side effects. There has been a demand in developing newer cancer agents that demonstrate selective cytoxicity with minimal effect on normal body tissue. Numerous studies have shown that marine organisms produce a wide range of halogenated compounds that possess cytotoxic properties, and hence can be a source of new drug hits or leads for cancer therapy. Halomon, a polyhalogenated monoterpene from Portieria hornemannii, displayed interesting activity against brain, renal and lung cancer tumours with selective/differential cytotoxicity. This inspired us to focus our project on halogenated monoterpenes isolated from the same Rhodophyta class as P. hornemannii but with particular attention to Plocamium species. Several metabolites have been isolated from P. cornutum, P. corallorhiza and P. suhrii that possess interesting cytotoxicities against a breast cancer cell line (MCF7) and an oesophageal cancer line (WHCO1). The aim of the project was therefore centred at isolating target compounds for preliminary structure-activity studies against a breast cancer cell line, and use this information to synthesize a series of analogues that are more stable than the natural products and yet as active using a fragment-based type approach to map out pharmacophoric elements. Five metabolites were isolated from P. cornutum and five from P. corallorhiza. Cell-based assays were conducted using an MTT assay kit against MCF7 and MDA-MB-231 breast cancer cell lines and (1E,3E,5S,6R)-1,5,6-trichloro-2-(dichloromethyl)-6-methylocta-1,3,7-triene, isolated from P. cornutum was the most active with IC50 values of 3.0 μM and 6.15 μM respectively. Introduction of a terminal aromatic ring to enhance stability, together with varying substituents (H, CH3, CF3, Br, CN, CHO, CHCl2) on position 7 of the molecule, gave rise to a series of cinnamate ester derivatives inspired by (1E,3E,5S,6R)-1,5,6-trichloro-2-(dichloromethyl)-6-methylocta-1,3,7-triene. The analogues were synthesized from their benzaldehyde precursors via Aldol condensation, esterification and Wittig reactions. Their carboxylic acid counterparts were synthesized by hydrolysis of the parent esters in an attempt to promote water solubilities of the analogues. Biological activity assays were then conducted with the cinnamate analogues against the MDA-MB-231 breast cancer cell line using an MTT assay kit. Ester derivatives with -CHO and -CHCl2 functionalities had IC50 values of 43.45 μM and 100.01 μM respectively whilst the other ester derivatives were inactive. It was concluded that either an aldehyde (-CHO) or gem-dichlorides (-CHCl2) is specifically required for cytotoxic activity to be observed. None of the carboxylic acids were active which could have been due to failure of the compounds to enter the breast cancer cells and reach the target site because of their polar nature. Compounds with -CHO and -CHCl2 functionalities were therefore selected for future SARs studies.
- Full Text:
The synthesis of fructooligosaccharides by the fructofuranosidase FopAp from Aspergillus niger
- Pindura, Mitchell Kingsley Chido
- Authors: Pindura, Mitchell Kingsley Chido
- Date: 2012
- Subjects: Aspergillus niger , Oligosaccharides
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4158 , http://hdl.handle.net/10962/d1018267
- Description: Fructooligosaccharides (FOS) are short-chain fructans with a terminal glucose moiety and are found naturally in many plant species. Besides their wide use as an alternative sweetener in food and beverage industry, FOS have shown great potential as neutraceuticals against diabetes, colon cancer and bowel disease. The uses of FOS are dependent on the degree of polymerisation that they exhibit. β-fructofuranosidase (FFase) and fructosyltransferase (FTase) enzymes are capable of synthesing FOS from carbohydrate raw materials such as chicory and sugar beet. The aim of this study was to investigate the synthesis of FOS of a pre-defined chain length, from sucrose, by the enzyme FopAp; a β-fructofuranosidase from Aspergillus niger. ATCC 20611. The crude enzyme FopAp was successfully purified, with a yield of 78.20 %, by ammonium sulphate precipitation and anion exchange chromatography. Two protein fractions, named FA and FB were shown to exhibit FFase activity. SDS PAGE analysis revealed two proteins with molecular weights of 112 kDa and 78 kDa, which were identified as a FFase and a hydrolase. Temperature and pH optima of 20 ºC and 9, respectively, were observed for the transfructosylation activity in the FFase. The purified FFase exhibited a half life of 1.5 hrs under optimal conditions. Substrate kinetic studies indicated a high hydrolytic activity at low sucrose concentrations, with Vmax and Km of 1.25 μmol/ml/min and 3.28 mM, respectively. Analysis by response surface methodology identified temperature and pH to be significant factors for the production of kestose and nystose, at a 95 % level of confidence. These findings were confirmed by neural networks constructed to identify optimal conditions of FOS synthesis.FOS synthesis was found to be optimal between pH 6 and pH 9 at 25 ºC. The factor of reaction time was found to be insignificant within the selected experimental constraints, for both FOS species. The findings of this investigation are very important as the foundations of a commercially viable synthetic process for the production of FOS.
- Full Text:
- Authors: Pindura, Mitchell Kingsley Chido
- Date: 2012
- Subjects: Aspergillus niger , Oligosaccharides
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4158 , http://hdl.handle.net/10962/d1018267
- Description: Fructooligosaccharides (FOS) are short-chain fructans with a terminal glucose moiety and are found naturally in many plant species. Besides their wide use as an alternative sweetener in food and beverage industry, FOS have shown great potential as neutraceuticals against diabetes, colon cancer and bowel disease. The uses of FOS are dependent on the degree of polymerisation that they exhibit. β-fructofuranosidase (FFase) and fructosyltransferase (FTase) enzymes are capable of synthesing FOS from carbohydrate raw materials such as chicory and sugar beet. The aim of this study was to investigate the synthesis of FOS of a pre-defined chain length, from sucrose, by the enzyme FopAp; a β-fructofuranosidase from Aspergillus niger. ATCC 20611. The crude enzyme FopAp was successfully purified, with a yield of 78.20 %, by ammonium sulphate precipitation and anion exchange chromatography. Two protein fractions, named FA and FB were shown to exhibit FFase activity. SDS PAGE analysis revealed two proteins with molecular weights of 112 kDa and 78 kDa, which were identified as a FFase and a hydrolase. Temperature and pH optima of 20 ºC and 9, respectively, were observed for the transfructosylation activity in the FFase. The purified FFase exhibited a half life of 1.5 hrs under optimal conditions. Substrate kinetic studies indicated a high hydrolytic activity at low sucrose concentrations, with Vmax and Km of 1.25 μmol/ml/min and 3.28 mM, respectively. Analysis by response surface methodology identified temperature and pH to be significant factors for the production of kestose and nystose, at a 95 % level of confidence. These findings were confirmed by neural networks constructed to identify optimal conditions of FOS synthesis.FOS synthesis was found to be optimal between pH 6 and pH 9 at 25 ºC. The factor of reaction time was found to be insignificant within the selected experimental constraints, for both FOS species. The findings of this investigation are very important as the foundations of a commercially viable synthetic process for the production of FOS.
- Full Text:
The synthesis of α-alkoxy and α-aminostannanes as precursors to Novel Chromium Fischer Carbenes
- Authors: Meyer, Annalene
- Date: 2012
- Subjects: Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4371 , http://hdl.handle.net/10962/d1005036 , Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Description: The present study involves the use of main group organometallics: organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are well stabilized by the π‐donor substituents such as alkoxy and amino groups and low oxidation state metals such as Group 6 (Chromium, Molybdenum or Tungsten). Carbenes are an important intermediate in the synthesis of a range of compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and successful characterisation of three α‐alkoxystannanes was achieved via nucleophilic addition of tributylstannyllithium to the respective aldehydes, followed by an immediate MOM protection of the resulting alcohol. Six α‐aminostanannes were synthesised, consisting of N‐BOC, N‐acetyl and N‐ethyl derivatives of pyrrolidine and piperidine, via α‐lithiation and subsequent tinlithium transmetallation in the presence of TMEDA. The ¹³C NMR analysis highlighted an interesting phenomenon of tin‐carbon coupling that revealed unique structural information of both types of stannanes. DFT analysis was completed on the series of stannanes; a predicted frequency analysis was obtained which complemented the experimental Infra‐red data in elucidation of the compounds. The α‐alkoxy and α‐aminostannanes provided stable precursors to the organolithiums required for the synthesis of the novel Fischer chromium carbenes. The organolithiums were obtained via tinlithium exchange at low temperatures, followed by the addition of chromium hexacarbonyl to form the acylpentacarbonyl‐chromate salt. Alkylation of this intermediate using a Meerwein salt, Me₃OBF₄, gave rise to the novel Fischer chromium carbene complexes. Fischer chromium carbenes derived from the two isomeric butyl and isobutyl stannanes and the two N‐ethyl α‐aminostannanes were successfully synthesised. The difficulty encountered in the purification of the Fischer carbene complexes hindered the full characterisation, due to the presence of a by‐product, tetrabutyltin.
- Full Text:
- Authors: Meyer, Annalene
- Date: 2012
- Subjects: Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4371 , http://hdl.handle.net/10962/d1005036 , Alkoxides , Organometallic compounds , Carbenes (Methylene compounds) , Chromium , Molybdenum , Tungsten , Organolithium compounds
- Description: The present study involves the use of main group organometallics: organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are well stabilized by the π‐donor substituents such as alkoxy and amino groups and low oxidation state metals such as Group 6 (Chromium, Molybdenum or Tungsten). Carbenes are an important intermediate in the synthesis of a range of compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and successful characterisation of three α‐alkoxystannanes was achieved via nucleophilic addition of tributylstannyllithium to the respective aldehydes, followed by an immediate MOM protection of the resulting alcohol. Six α‐aminostanannes were synthesised, consisting of N‐BOC, N‐acetyl and N‐ethyl derivatives of pyrrolidine and piperidine, via α‐lithiation and subsequent tinlithium transmetallation in the presence of TMEDA. The ¹³C NMR analysis highlighted an interesting phenomenon of tin‐carbon coupling that revealed unique structural information of both types of stannanes. DFT analysis was completed on the series of stannanes; a predicted frequency analysis was obtained which complemented the experimental Infra‐red data in elucidation of the compounds. The α‐alkoxy and α‐aminostannanes provided stable precursors to the organolithiums required for the synthesis of the novel Fischer chromium carbenes. The organolithiums were obtained via tinlithium exchange at low temperatures, followed by the addition of chromium hexacarbonyl to form the acylpentacarbonyl‐chromate salt. Alkylation of this intermediate using a Meerwein salt, Me₃OBF₄, gave rise to the novel Fischer chromium carbene complexes. Fischer chromium carbenes derived from the two isomeric butyl and isobutyl stannanes and the two N‐ethyl α‐aminostannanes were successfully synthesised. The difficulty encountered in the purification of the Fischer carbene complexes hindered the full characterisation, due to the presence of a by‐product, tetrabutyltin.
- Full Text:
The synthesis, photophysical and dielectric properties of ball-type dinuclear zinc phthalocyanine
- Canlıca, Mevlüde, Altındal, Ahmet, Nyokong, Tebello
- Authors: Canlıca, Mevlüde , Altındal, Ahmet , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243532 , vital:51161 , xlink:href="https://doi.org/10.1142/S1088424612500836"
- Description: The synthesis of ball-type dinuclear Zn(II) phthalocyanine containing four 4,4′-(9H-fluorene-9,9-diyl)diphenol substituents at the non-peripheral position is presented. The structure of the synthesized compound was characterized using elemental analyzes, and UV-vis, FT-IR, 1H NMR and mass spectroscopies. The ΦF value was 0.16 and ΦT value was 0.72. The complex showed reasonably long triplet lifetimes with τT 7210 μs in DMSO. The frequency and temperature dependence of the dielectric properties of ZnPc were also investigated in the frequency range of 40–105 Hz and in the temperature range of 300–440 °K. It has been observed that both dielectric constant ε′ and dielectric loss ε″ decrease with the rise in frequency as they increase with the rise in temperature. The decrease in ε′ with increasing frequency is attributed to the fact that as the frequency increases, the polarizability contribution from orientation sources decreases and finally disappears.
- Full Text:
- Authors: Canlıca, Mevlüde , Altındal, Ahmet , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243532 , vital:51161 , xlink:href="https://doi.org/10.1142/S1088424612500836"
- Description: The synthesis of ball-type dinuclear Zn(II) phthalocyanine containing four 4,4′-(9H-fluorene-9,9-diyl)diphenol substituents at the non-peripheral position is presented. The structure of the synthesized compound was characterized using elemental analyzes, and UV-vis, FT-IR, 1H NMR and mass spectroscopies. The ΦF value was 0.16 and ΦT value was 0.72. The complex showed reasonably long triplet lifetimes with τT 7210 μs in DMSO. The frequency and temperature dependence of the dielectric properties of ZnPc were also investigated in the frequency range of 40–105 Hz and in the temperature range of 300–440 °K. It has been observed that both dielectric constant ε′ and dielectric loss ε″ decrease with the rise in frequency as they increase with the rise in temperature. The decrease in ε′ with increasing frequency is attributed to the fact that as the frequency increases, the polarizability contribution from orientation sources decreases and finally disappears.
- Full Text:
The treatment of brewery effluent using an integrated high rate algal ponding system
- Authors: Cilliers, Anneke
- Date: 2012
- Subjects: Water -- Purification -- South Africa , Algae -- Biotechnology , Algae culture , Algae -- Economic aspects
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5331 , http://hdl.handle.net/10962/d1005177 , Water -- Purification -- South Africa , Algae -- Biotechnology , Algae culture , Algae -- Economic aspects
- Description: The application of high rate algal ponds (HRAP) in the treatment of brewery effluent that met the South African Department of Water Affairs and Forestry's (DWAF) general limits for discharge into a natural water resource of 1998 were tested during a lO-month baseline phase, followed by an 11-month optimization phase. The objective of the baseline phase was to monitor the seasonal performance of HRAPs. The hydraulic retention time (HRT) fluctuated between 11.16 d and 12.00 d in HRAPs. The chemical oxygen demand (COD) increased from 130.12 ± 6.94 mg/L (post-AD), to 171.21 ± 7.99 mg/L (post-HRAP) . The presence of algal cells and evaporation contributed towards an increase in post-HRAP COD. The ammonia (NH₄-N) concentration decreased from 46.59 ± 2.47 mg/L (post-AD), to 1.08 ± 0.12 mg/L (post-HRAP). The nitrite (NO₂- N) concentration remained below 1.00 mg/L in post-pilot plant AD, post-PFP and post-HRAP effluent. The phosphate (PO₄-P) concentration decreased from 29.81 ± 1.39 mg/L (post-AD) to 17.30 ± 1.16 mg/L PO₄-P. The objective of the optimization phase was to manipulate the HRT to achieve the maximum treatment rate that met the DWAF general limits for discharge into a natural water resource of 1998. Nitrogen (as NH₄-N, NO₃-N, NO₂-N) removal efficiency was used as an indicator of nutrient removal success. HRT was influenced by season. The optimal HRT for autumn was 4.30 d at a temperature of 20.53ºC in HRAP A2 (heated) and 18.96ºC in HRAP B2 (ambient). The optimal HRT for summer was 2.74 d at 29.90ºC in HRAP A2 (heated) and 26.36ºC in HRAP B2 (ambient). The COD decreased from 152.33 ± 4.85 mg/L (post-AD) to 95 .00 ± 3.75 mg/L (post-HRAP A2), and to 100.82 ± 5.93 mg/L (post-HRAP B2). The incoming NH₄-N concentration decreased from 42.53 ± 1.38 mg/ L (post-AD), to 1.70 ± 0.81 mg/ L (post-HRAP) . The nitrate (NO₃-N) concentration post-HRAP was 12 - 14 mg/L. The main methods for NH₄-N removal were probably NH₄-N volatilization through algal uptake. HRAPs were able to lower nitrogen and phosphorous concentrations to within the DWAF limits under normal operating conditions. It is recommended that HRAP treated brewery wastewater be used for irrigation after salt removal, or alternatively, for groundwater recharge . Regulatory exemptions would be required for higher than permitted COD and EC concentrations to enable these actions.
- Full Text:
- Authors: Cilliers, Anneke
- Date: 2012
- Subjects: Water -- Purification -- South Africa , Algae -- Biotechnology , Algae culture , Algae -- Economic aspects
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5331 , http://hdl.handle.net/10962/d1005177 , Water -- Purification -- South Africa , Algae -- Biotechnology , Algae culture , Algae -- Economic aspects
- Description: The application of high rate algal ponds (HRAP) in the treatment of brewery effluent that met the South African Department of Water Affairs and Forestry's (DWAF) general limits for discharge into a natural water resource of 1998 were tested during a lO-month baseline phase, followed by an 11-month optimization phase. The objective of the baseline phase was to monitor the seasonal performance of HRAPs. The hydraulic retention time (HRT) fluctuated between 11.16 d and 12.00 d in HRAPs. The chemical oxygen demand (COD) increased from 130.12 ± 6.94 mg/L (post-AD), to 171.21 ± 7.99 mg/L (post-HRAP) . The presence of algal cells and evaporation contributed towards an increase in post-HRAP COD. The ammonia (NH₄-N) concentration decreased from 46.59 ± 2.47 mg/L (post-AD), to 1.08 ± 0.12 mg/L (post-HRAP). The nitrite (NO₂- N) concentration remained below 1.00 mg/L in post-pilot plant AD, post-PFP and post-HRAP effluent. The phosphate (PO₄-P) concentration decreased from 29.81 ± 1.39 mg/L (post-AD) to 17.30 ± 1.16 mg/L PO₄-P. The objective of the optimization phase was to manipulate the HRT to achieve the maximum treatment rate that met the DWAF general limits for discharge into a natural water resource of 1998. Nitrogen (as NH₄-N, NO₃-N, NO₂-N) removal efficiency was used as an indicator of nutrient removal success. HRT was influenced by season. The optimal HRT for autumn was 4.30 d at a temperature of 20.53ºC in HRAP A2 (heated) and 18.96ºC in HRAP B2 (ambient). The optimal HRT for summer was 2.74 d at 29.90ºC in HRAP A2 (heated) and 26.36ºC in HRAP B2 (ambient). The COD decreased from 152.33 ± 4.85 mg/L (post-AD) to 95 .00 ± 3.75 mg/L (post-HRAP A2), and to 100.82 ± 5.93 mg/L (post-HRAP B2). The incoming NH₄-N concentration decreased from 42.53 ± 1.38 mg/ L (post-AD), to 1.70 ± 0.81 mg/ L (post-HRAP) . The nitrate (NO₃-N) concentration post-HRAP was 12 - 14 mg/L. The main methods for NH₄-N removal were probably NH₄-N volatilization through algal uptake. HRAPs were able to lower nitrogen and phosphorous concentrations to within the DWAF limits under normal operating conditions. It is recommended that HRAP treated brewery wastewater be used for irrigation after salt removal, or alternatively, for groundwater recharge . Regulatory exemptions would be required for higher than permitted COD and EC concentrations to enable these actions.
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The trophic ecology of parrotfish of Zanzibar application of stable isotope analysis
- Plass-Johnson, Jeremiah Grahm
- Authors: Plass-Johnson, Jeremiah Grahm
- Date: 2012
- Subjects: Parrotfishes -- Tanzania -- Zanzibar , Parrotfishes , Parrotfishes -- Ecology -- Tanzania -- Zanzibar , Parrotfishes -- Behavior -- Tanzania -- Zanzibar , Parrotfishes -- Food -- Tanzania -- Zanzibar , Scleractinia -- Tanzania -- Zanzibar , Algae -- Tanzania -- Zanzibar , Coral reefs and islands -- Tanzania -- Zanzibar , Coral reef fishes -- Tanzania -- Zanzibar , Stable isotopes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5789 , http://hdl.handle.net/10962/d1005477 , Parrotfishes -- Tanzania -- Zanzibar , Parrotfishes , Parrotfishes -- Ecology -- Tanzania -- Zanzibar , Parrotfishes -- Behavior -- Tanzania -- Zanzibar , Parrotfishes -- Food -- Tanzania -- Zanzibar , Scleractinia -- Tanzania -- Zanzibar , Algae -- Tanzania -- Zanzibar , Coral reefs and islands -- Tanzania -- Zanzibar , Coral reef fishes -- Tanzania -- Zanzibar , Stable isotopes
- Description: Parrotfish are a critical component of the herbivore functional group on tropical coral reefs around the world because they mediate competition that occurs between algae and scleractinian corals. Also, because of their feeding technique, which consists of rasping at the substratum with their beak-like teeth, they play an important role in carbonate turnover and the clearing of reef surface area for the settlement of new sessile organisms. Because of these roles, parrotfishes are an important structuring component of coral reef communities. However, individual species can play different roles depending on their physiology, behaviour and ecology. Despite the possible ecological differences that may exist amongst species, specific roles of the fishes remain unclear as the group is most often studied at higher community levels. This thesis applied stable isotope analysis to differing levels of organisation within a parrotfish community to help elucidate their trophic ecology on coral reefs in Zanzibar. Firstly, blood and muscle tissues were compared to identify differences in their isotope signatures. In other organisms, blood turns over faster than muscle tissue so that muscle tissue represents the diet as integrated over a longer period of time. In most species of parrotfish the blood and muscle δ¹³C signatures were not found to be significantly different, but the δ¹⁵N signatures were significantly different between tissues. This indicated that the δ¹³C signature of both tissues would reveal similar dietary information. Conversely, differences in the δ¹⁵N signature indicated that the nitrogen relationship between tissues was more complicated. Secondly, spatial variability in parrotfish, coral, detritus and macroalgae isotope signatures was assessed at different scales. In macroalgae and coral tissues (zooxanthellae and polyp treated separately), the δ¹³C signatures were shown to differ with depth, presumably because of changes in photosynthetic processes related to depth-associated changes in light. While δ¹⁵N signatures were not affected by depth, all organisms showed enrichment at the Nyange reef, the closest reef to the capital of Zanzibar, Stone Town, presumably reflecting the effects of sewage outfall. These results show that processes that impact the δ¹⁵N signatures of primary producers (macroalgae and zooxanthellae) can be traced to higher trophic levels (coral polyps and fish). Lastly, δ¹³C and δ¹⁵N signatures were used to identify ontogenetic dietary changes in multiple species of parrotfish. Four of the species showed stages that varied from the diets that are normally assumed on the basis of their dentition and feeding technique. This indicates that functional roles based on taxonomy or morphology may fail to include possible ontogenetic dietary changes, and may also fail to elucidate the full impact a species could have on coral reef communities. The conclusions from these studies indicate that the species-specific ecological role of parrotfish in coral reef communities can be complex within and between species, and may differ amongst reefs. In light of the natural and anthropogenic pressures that affect coral reef systems, management decisions based on a more complete understanding of the role of these fish in coral reef communities will help decisions that maintain resilience in these fragile systems.
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- Authors: Plass-Johnson, Jeremiah Grahm
- Date: 2012
- Subjects: Parrotfishes -- Tanzania -- Zanzibar , Parrotfishes , Parrotfishes -- Ecology -- Tanzania -- Zanzibar , Parrotfishes -- Behavior -- Tanzania -- Zanzibar , Parrotfishes -- Food -- Tanzania -- Zanzibar , Scleractinia -- Tanzania -- Zanzibar , Algae -- Tanzania -- Zanzibar , Coral reefs and islands -- Tanzania -- Zanzibar , Coral reef fishes -- Tanzania -- Zanzibar , Stable isotopes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5789 , http://hdl.handle.net/10962/d1005477 , Parrotfishes -- Tanzania -- Zanzibar , Parrotfishes , Parrotfishes -- Ecology -- Tanzania -- Zanzibar , Parrotfishes -- Behavior -- Tanzania -- Zanzibar , Parrotfishes -- Food -- Tanzania -- Zanzibar , Scleractinia -- Tanzania -- Zanzibar , Algae -- Tanzania -- Zanzibar , Coral reefs and islands -- Tanzania -- Zanzibar , Coral reef fishes -- Tanzania -- Zanzibar , Stable isotopes
- Description: Parrotfish are a critical component of the herbivore functional group on tropical coral reefs around the world because they mediate competition that occurs between algae and scleractinian corals. Also, because of their feeding technique, which consists of rasping at the substratum with their beak-like teeth, they play an important role in carbonate turnover and the clearing of reef surface area for the settlement of new sessile organisms. Because of these roles, parrotfishes are an important structuring component of coral reef communities. However, individual species can play different roles depending on their physiology, behaviour and ecology. Despite the possible ecological differences that may exist amongst species, specific roles of the fishes remain unclear as the group is most often studied at higher community levels. This thesis applied stable isotope analysis to differing levels of organisation within a parrotfish community to help elucidate their trophic ecology on coral reefs in Zanzibar. Firstly, blood and muscle tissues were compared to identify differences in their isotope signatures. In other organisms, blood turns over faster than muscle tissue so that muscle tissue represents the diet as integrated over a longer period of time. In most species of parrotfish the blood and muscle δ¹³C signatures were not found to be significantly different, but the δ¹⁵N signatures were significantly different between tissues. This indicated that the δ¹³C signature of both tissues would reveal similar dietary information. Conversely, differences in the δ¹⁵N signature indicated that the nitrogen relationship between tissues was more complicated. Secondly, spatial variability in parrotfish, coral, detritus and macroalgae isotope signatures was assessed at different scales. In macroalgae and coral tissues (zooxanthellae and polyp treated separately), the δ¹³C signatures were shown to differ with depth, presumably because of changes in photosynthetic processes related to depth-associated changes in light. While δ¹⁵N signatures were not affected by depth, all organisms showed enrichment at the Nyange reef, the closest reef to the capital of Zanzibar, Stone Town, presumably reflecting the effects of sewage outfall. These results show that processes that impact the δ¹⁵N signatures of primary producers (macroalgae and zooxanthellae) can be traced to higher trophic levels (coral polyps and fish). Lastly, δ¹³C and δ¹⁵N signatures were used to identify ontogenetic dietary changes in multiple species of parrotfish. Four of the species showed stages that varied from the diets that are normally assumed on the basis of their dentition and feeding technique. This indicates that functional roles based on taxonomy or morphology may fail to include possible ontogenetic dietary changes, and may also fail to elucidate the full impact a species could have on coral reef communities. The conclusions from these studies indicate that the species-specific ecological role of parrotfish in coral reef communities can be complex within and between species, and may differ amongst reefs. In light of the natural and anthropogenic pressures that affect coral reef systems, management decisions based on a more complete understanding of the role of these fish in coral reef communities will help decisions that maintain resilience in these fragile systems.
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The use of hot and cold high pressure homogenization to enhance the loading capacity and encapsulation efficiency of nanostructured lipid carriers for the hydrophilic antiretroviral drug, didanosine for potential administration to paediatric patients
- Kasongo, Kasongo W, Müller, Rainer H, Walker, Roderick B
- Authors: Kasongo, Kasongo W , Müller, Rainer H , Walker, Roderick B
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184087 , vital:44170 , xlink:href="https://doi.org/10.3109/10837450.2010.542163"
- Description: A major obstacle to the application of nanostructured lipid carriers (NLCs) as carriers for hydrophilic drugs is the limited loading capacity (LC) and encapsulation efficiency (EE) of NLCs for these molecules. The purpose of this research was to design and implement a strategy to enhance the LC and EE of NLCs for the hydrophilic drug, didanosine (DDI). DDI was dispersed in Transcutol® HP and the particle size of DDI in the liquid lipid was reduced gradually using hot high pressure homogenization (HPH). The product obtained thereafter was added to Precirol® ATO 5 and the hot mixture was immediately dried using liquid nitrogen. The dried materials were then ground and passed through a 200 μm sieve and the solid lipid particles were dispersed in a surfactant solution and subsequently used to manufacture DDI-loaded NLCs using cold HPH. The LC and EE of NLCs for DDI manufactured using the new strategy were 3.39 ± 0.63% and 51.58 ± 1.31%, respectively, compared to 0.079 ± 0.001% and 32.45 ± 0.08%, respectively, obtained when DDI-loaded NLCs were produced using conventional hot HPH. The enhanced LC and EE for DDI make NLCs a potential technology for the oral administration of DDI to paediatric patients.
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- Authors: Kasongo, Kasongo W , Müller, Rainer H , Walker, Roderick B
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184087 , vital:44170 , xlink:href="https://doi.org/10.3109/10837450.2010.542163"
- Description: A major obstacle to the application of nanostructured lipid carriers (NLCs) as carriers for hydrophilic drugs is the limited loading capacity (LC) and encapsulation efficiency (EE) of NLCs for these molecules. The purpose of this research was to design and implement a strategy to enhance the LC and EE of NLCs for the hydrophilic drug, didanosine (DDI). DDI was dispersed in Transcutol® HP and the particle size of DDI in the liquid lipid was reduced gradually using hot high pressure homogenization (HPH). The product obtained thereafter was added to Precirol® ATO 5 and the hot mixture was immediately dried using liquid nitrogen. The dried materials were then ground and passed through a 200 μm sieve and the solid lipid particles were dispersed in a surfactant solution and subsequently used to manufacture DDI-loaded NLCs using cold HPH. The LC and EE of NLCs for DDI manufactured using the new strategy were 3.39 ± 0.63% and 51.58 ± 1.31%, respectively, compared to 0.079 ± 0.001% and 32.45 ± 0.08%, respectively, obtained when DDI-loaded NLCs were produced using conventional hot HPH. The enhanced LC and EE for DDI make NLCs a potential technology for the oral administration of DDI to paediatric patients.
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