Synthesis, density functional theory, molecular dynamics and electrochemical studies of 3-thiopheneacetic acid-capped gold nanoparticles
- Sosibo, Ndabenhle M, Mdluli, Phumlane S, Mashazi, Philani N, Dyan, Busiswa, Revaprasadu, Neerish, Nyokong, Tebello, Tshikhudo, Robert T, Skepu, Amanda, Van Der Lingen, Elma
- Authors: Sosibo, Ndabenhle M , Mdluli, Phumlane S , Mashazi, Philani N , Dyan, Busiswa , Revaprasadu, Neerish , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , Van Der Lingen, Elma
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246446 , vital:51477 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.09.057"
- Description: Gold nanoparticles capped with a bifunctional ligand, 3-thiopheneacetic acid (3-TAA) were synthesised by borohydride reduction at room temperature. The transmission electron microscopy (TEM) analysis showed that the particle aggregates and had semi-linear partial linkages that could be attributed to multi-modal binding of the ligand with various gold nanoparticles through the terminal thiolether (–S–) group and oxygen of the carboxylic (–COOH) group. This bimodal interaction led to limited stability of the resultant nanoparticles when tested using highly electrolytic media. To investigate further, density functional theory (DFT) quantum chemical and molecular dynamic calculations were conducted. The energetically favorable binding modes of the ligand to gold nanoparticle surfaces using the Gaussian program were studied. The DFT results showed kinetic stability of Au–3-TAA–Au interactions leading to inter-particle coupling or aggregation. Electrochemical analysis of the resultant nature of the capping agent revealed that 3-thiopheneacetic acid did not form a polymer during the preparation of Au–3-TAA. The cyclic voltammograms of Au–3-TAA nanoparticles coated glassy carbon electrode showed a typical gold character with the oxidation and reduction peaks at 1.4 V and 0.9 V, respectively.
- Full Text:
- Date Issued: 2012
- Authors: Sosibo, Ndabenhle M , Mdluli, Phumlane S , Mashazi, Philani N , Dyan, Busiswa , Revaprasadu, Neerish , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , Van Der Lingen, Elma
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246446 , vital:51477 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.09.057"
- Description: Gold nanoparticles capped with a bifunctional ligand, 3-thiopheneacetic acid (3-TAA) were synthesised by borohydride reduction at room temperature. The transmission electron microscopy (TEM) analysis showed that the particle aggregates and had semi-linear partial linkages that could be attributed to multi-modal binding of the ligand with various gold nanoparticles through the terminal thiolether (–S–) group and oxygen of the carboxylic (–COOH) group. This bimodal interaction led to limited stability of the resultant nanoparticles when tested using highly electrolytic media. To investigate further, density functional theory (DFT) quantum chemical and molecular dynamic calculations were conducted. The energetically favorable binding modes of the ligand to gold nanoparticle surfaces using the Gaussian program were studied. The DFT results showed kinetic stability of Au–3-TAA–Au interactions leading to inter-particle coupling or aggregation. Electrochemical analysis of the resultant nature of the capping agent revealed that 3-thiopheneacetic acid did not form a polymer during the preparation of Au–3-TAA. The cyclic voltammograms of Au–3-TAA nanoparticles coated glassy carbon electrode showed a typical gold character with the oxidation and reduction peaks at 1.4 V and 0.9 V, respectively.
- Full Text:
- Date Issued: 2012
The direct use value of municipal commonage goods and services to urban households in the Eastern Cape, South Africa
- Davenport, Nicholas A, Shackleton, Charlie M, Gambiza, James
- Authors: Davenport, Nicholas A , Shackleton, Charlie M , Gambiza, James
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181071 , vital:43696 , xlink:href="https://doi.org/10.1016/j.landusepol.2011.09.008"
- Description: To redress past racial discrepancies in ownership and tenure, the ANC government of South Africa initiated programmes to make land accessible to the previously disadvantaged. A key component of the national land reform programme was the provision of commonage lands to urban municipalities for use by the urban poor. However, there has been no assessment of the contribution that urban commonage makes to previously disadvantaged households. This study assessed the economic benefits of the commonage programme to local households, through an in-depth survey of 90 households across three small towns in the Eastern Cape of South Africa. We examined the marketed and non-marketed consumptive direct-use values of land-based livelihoods on commonage, calculated via the ‘own reported values’ approach. The results indicate that a proportion of South Africa's urban population rely to some degree on municipal commonage for part of their livelihoods. Commonage contributions to total livelihood incomes ranged between 14 and 20%. If the contributions from commonage were excluded, the incomes of over 10% of households in each study town would drop below the poverty line. Overall, the value of harvests from commonage was worth over R1 000 (US$ 142) per hectare per year and over R4.7 million (US$ 0.68 million) per commonage per year. However, the extent and nature of use and reliance was not uniform among households, so that we developed a typology of commonage users, with four types being identified. However, rapidly growing urban populations and high levels of poverty potentially threaten the sustainability of commonage resource use. Yet the national land reform programme focuses largely on the transfer of land to municipalities and not on sustainable management. Municipalities, in turn, invest relatively little in commonage management, and the little they do is focussed on livestock production. Non-timber forest products are not considered at all, even though this study shows that they are a vital resource for the urban poor, notably for energy and construction materials.
- Full Text:
- Date Issued: 2012
- Authors: Davenport, Nicholas A , Shackleton, Charlie M , Gambiza, James
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181071 , vital:43696 , xlink:href="https://doi.org/10.1016/j.landusepol.2011.09.008"
- Description: To redress past racial discrepancies in ownership and tenure, the ANC government of South Africa initiated programmes to make land accessible to the previously disadvantaged. A key component of the national land reform programme was the provision of commonage lands to urban municipalities for use by the urban poor. However, there has been no assessment of the contribution that urban commonage makes to previously disadvantaged households. This study assessed the economic benefits of the commonage programme to local households, through an in-depth survey of 90 households across three small towns in the Eastern Cape of South Africa. We examined the marketed and non-marketed consumptive direct-use values of land-based livelihoods on commonage, calculated via the ‘own reported values’ approach. The results indicate that a proportion of South Africa's urban population rely to some degree on municipal commonage for part of their livelihoods. Commonage contributions to total livelihood incomes ranged between 14 and 20%. If the contributions from commonage were excluded, the incomes of over 10% of households in each study town would drop below the poverty line. Overall, the value of harvests from commonage was worth over R1 000 (US$ 142) per hectare per year and over R4.7 million (US$ 0.68 million) per commonage per year. However, the extent and nature of use and reliance was not uniform among households, so that we developed a typology of commonage users, with four types being identified. However, rapidly growing urban populations and high levels of poverty potentially threaten the sustainability of commonage resource use. Yet the national land reform programme focuses largely on the transfer of land to municipalities and not on sustainable management. Municipalities, in turn, invest relatively little in commonage management, and the little they do is focussed on livestock production. Non-timber forest products are not considered at all, even though this study shows that they are a vital resource for the urban poor, notably for energy and construction materials.
- Full Text:
- Date Issued: 2012
The effect of harvesting approaches on fruit yield, embelin concentration and regrowth dynamics of the forest shrub, Embelia tsjeriam-cottam, in central India
- Pandey, Ashok K, Shackleton, Charlie M
- Authors: Pandey, Ashok K , Shackleton, Charlie M
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181094 , vital:43698 , xlink:href="https://doi.org/10.1016/j.foreco.2011.11.015"
- Description: Embelia tsjeriam-cottam Roem and Schult A. DC. (Myrsinaceae), popularly known as Vaividang, is a vulnerable forest species because of the high demand of fruits for medicinal purposes. It is in great demand in ayurveda and the pharmaceutical industry (>100 t/yr), which has imposed tremendous pressure on some natural populations. The fruits contain embelin (a benzoquinone derivative), which has wide clinical applications. Considering the importance, growing use and decreasing populations in some areas of its natural habitat, a study on development of sustainable harvesting practices of E. tsjeriam-cottam fruits was conducted in Chhattisgarh, in central India. Experiments were laid out in Dhamtari, Marvahi and Bilaspur forest divisions of the state covering both protected and open forests in a randomized design with three replications. At each site, quadrats of 40 × 20 m were laid out to study the effect of two fruit harvesting methods and four harvesting intensities on fruit yield, and regeneration of the species. Fruits were analyzed for their embelin content by HPLC method. This study is the first to experimentally assess the consequences of harvesting of E. tsjeriam-cottam fruits from India. It was found that up to 70% fruits could be hand plucked at the right time of maturity (December) to obtain quality produce without impacting the current population size. Since every year is not a good fruiting year, it is difficult to develop universal harvest regime for sustainable management of E. tsjeriam-cottam. The embelin content increased as fruits ripened, ranging from 1.01% to 5.63%. The adoption of sustainable harvesting practices will be helpful in sustainable management of E. tsjeriam-cottam and also provide income and livelihood opportunities to rural people on a sustainable basis.
- Full Text:
- Date Issued: 2012
- Authors: Pandey, Ashok K , Shackleton, Charlie M
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181094 , vital:43698 , xlink:href="https://doi.org/10.1016/j.foreco.2011.11.015"
- Description: Embelia tsjeriam-cottam Roem and Schult A. DC. (Myrsinaceae), popularly known as Vaividang, is a vulnerable forest species because of the high demand of fruits for medicinal purposes. It is in great demand in ayurveda and the pharmaceutical industry (>100 t/yr), which has imposed tremendous pressure on some natural populations. The fruits contain embelin (a benzoquinone derivative), which has wide clinical applications. Considering the importance, growing use and decreasing populations in some areas of its natural habitat, a study on development of sustainable harvesting practices of E. tsjeriam-cottam fruits was conducted in Chhattisgarh, in central India. Experiments were laid out in Dhamtari, Marvahi and Bilaspur forest divisions of the state covering both protected and open forests in a randomized design with three replications. At each site, quadrats of 40 × 20 m were laid out to study the effect of two fruit harvesting methods and four harvesting intensities on fruit yield, and regeneration of the species. Fruits were analyzed for their embelin content by HPLC method. This study is the first to experimentally assess the consequences of harvesting of E. tsjeriam-cottam fruits from India. It was found that up to 70% fruits could be hand plucked at the right time of maturity (December) to obtain quality produce without impacting the current population size. Since every year is not a good fruiting year, it is difficult to develop universal harvest regime for sustainable management of E. tsjeriam-cottam. The embelin content increased as fruits ripened, ranging from 1.01% to 5.63%. The adoption of sustainable harvesting practices will be helpful in sustainable management of E. tsjeriam-cottam and also provide income and livelihood opportunities to rural people on a sustainable basis.
- Full Text:
- Date Issued: 2012
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:
- Date Issued: 2012
- 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:
- Date Issued: 2012
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:
- Date Issued: 2012
- 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:
- Date Issued: 2012
The way forward with ecosystem-based management in tropical contexts: Reconciling with existing management systems
- Aswani, Shankar, Christie, Patrick, Muthiga, Nyawira A, Mahon, Robin, Primavera, Jurgenne H, Cramer, Lori A, Barbier, Edward B, Granek, Elise F, Kennedy, Chris J, Wolanski, Eric, Hacker, Sally
- Authors: Aswani, Shankar , Christie, Patrick , Muthiga, Nyawira A , Mahon, Robin , Primavera, Jurgenne H , Cramer, Lori A , Barbier, Edward B , Granek, Elise F , Kennedy, Chris J , Wolanski, Eric , Hacker, Sally
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/422693 , vital:71969 , xlink:href="https://doi.org/10.1016/j.marpol.2011.02.014"
- Description: This paper discusses some of the challenges and opportunities that can arise when implementing ecosystem-based management (EBM) in tropical nations. EBM creates a new series of challenges, problems, and opportunities that must be considered in light of existing governance and management frameworks in a local context. The paper presents five case studies from different parts of the tropical world, including Oceania, insular and continental Southeast Asia, East Africa, and the Caribbean, which illustrate that the implementation of EBM in watershed and marine ecosystems offers a new series of challenges and opportunities for its inclusion with existing forms of environmental governance and management. The paper suggests that EBM is best thought of as an expansion of customary management (CM) and integrated coastal management (ICM), rather than a paradigm shift, and that it has certain benefits that are worth integrating into existing systems when possible. The paper concludes that the cultural and institutional context of CM as well as the experience, technical skills, and legal basis that serve ICM programs are logical platforms from which to build EBM programs. Some guidelines for creating hybrid management regimes are suggested. In sum, declining marine species and ecosystems require urgent action, necessitating utilization of existing paradigms such as ICM and CM as a foundation for building EBM.
- Full Text:
- Date Issued: 2012
- Authors: Aswani, Shankar , Christie, Patrick , Muthiga, Nyawira A , Mahon, Robin , Primavera, Jurgenne H , Cramer, Lori A , Barbier, Edward B , Granek, Elise F , Kennedy, Chris J , Wolanski, Eric , Hacker, Sally
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/422693 , vital:71969 , xlink:href="https://doi.org/10.1016/j.marpol.2011.02.014"
- Description: This paper discusses some of the challenges and opportunities that can arise when implementing ecosystem-based management (EBM) in tropical nations. EBM creates a new series of challenges, problems, and opportunities that must be considered in light of existing governance and management frameworks in a local context. The paper presents five case studies from different parts of the tropical world, including Oceania, insular and continental Southeast Asia, East Africa, and the Caribbean, which illustrate that the implementation of EBM in watershed and marine ecosystems offers a new series of challenges and opportunities for its inclusion with existing forms of environmental governance and management. The paper suggests that EBM is best thought of as an expansion of customary management (CM) and integrated coastal management (ICM), rather than a paradigm shift, and that it has certain benefits that are worth integrating into existing systems when possible. The paper concludes that the cultural and institutional context of CM as well as the experience, technical skills, and legal basis that serve ICM programs are logical platforms from which to build EBM programs. Some guidelines for creating hybrid management regimes are suggested. In sum, declining marine species and ecosystems require urgent action, necessitating utilization of existing paradigms such as ICM and CM as a foundation for building EBM.
- Full Text:
- Date Issued: 2012
Unquenched fluorescence lifetime for β-phenylthio substituted zinc phthalocyanine upon conjugation to gold nanoparticles
- Forteath, Shaun, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
- Full Text:
- Date Issued: 2012
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
- Full Text:
- Date Issued: 2012