A comparative study on the sensitive detection of hydroxyl radical using thiol-capped CdTe and CdTe/ZnS quantum dots
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242778 , vital:51077 , xlink:href="https://doi.org/10.1007/s10895-012-1089-2"
- Description: Four types of water-soluble luminescent quantum dots (QDs) whose surface was functionlaized with thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), or glutathione (GSH), were investigated for the sensitive and selective detection of hydroxyl radical (●OH) in aqueous media. It was found that the type of capping agent and QD influenced the sensitivity of the probe. The order of sensitivity of the probe was: GSH-CdTe@ZnS > MPA-CdTe@ZnS > TGA-CdTe > MPA-CdTe QDs. Under the optimum conditions, a limit of detection as low as 8.5 × 10-8 M was obtained using GSH-CdTe@ZnS. The effects of foreign reactive oxygen species and the Fenton reactants and products as possible interferences on the proposed probe were negligible for CdTe@ZnS QDs. Besides, experimental results indicated that CdTe@ZnS QDs were more attractive for the selective recognition of ●OH than CdTe QDs. The mechanistic reaction pathway between the QDs and ●OH is proposed.
- Full Text:
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242778 , vital:51077 , xlink:href="https://doi.org/10.1007/s10895-012-1089-2"
- Description: Four types of water-soluble luminescent quantum dots (QDs) whose surface was functionlaized with thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), or glutathione (GSH), were investigated for the sensitive and selective detection of hydroxyl radical (●OH) in aqueous media. It was found that the type of capping agent and QD influenced the sensitivity of the probe. The order of sensitivity of the probe was: GSH-CdTe@ZnS > MPA-CdTe@ZnS > TGA-CdTe > MPA-CdTe QDs. Under the optimum conditions, a limit of detection as low as 8.5 × 10-8 M was obtained using GSH-CdTe@ZnS. The effects of foreign reactive oxygen species and the Fenton reactants and products as possible interferences on the proposed probe were negligible for CdTe@ZnS QDs. Besides, experimental results indicated that CdTe@ZnS QDs were more attractive for the selective recognition of ●OH than CdTe QDs. The mechanistic reaction pathway between the QDs and ●OH is proposed.
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How do HIV and AIDS impact the use of natural resources by poor rural populations?: The case of wild animal products
- Kaschula, Sarah, Shackleton, Charlie M
- Authors: Kaschula, Sarah , Shackleton, Charlie M
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182344 , vital:43822 , xlink:href="https://hdl.handle.net/10520/EJC97203"
- Description: As a result of heightened financial and food insecurity, populations adversely affected by HIV and/or AIDS may be more likely to utilise wild natural resources to supplement their diet and livelihoods. Should this effect be pronounced, HIV and AIDS may pose a serious environmental threat. We explored the hypothesis that the presence of factors in the household, such as chronic illness in and recent mortality of individuals in a high HIV-risk age group, as well as the fostering of orphans, are associated with increased utilisation of wild animal products (WAPs) at the household level. We randomly surveyed 519 households from four sites in rural South Africa, recording household socio-economic status, the utilisation of wild animal products and health and demographic factors attributed to HIV or AIDS. Binary logistic regressions were used to test if households with markers of HIV and/or AIDS affliction were more likely to have a higher incidence and frequency of WAP utilisation relative to non-afflicted households, after adjusting for socio-economic and demographic variables. We found that, although households with markers of HIV and/or AIDS were generally poorer and had higher dependency ratios, there was no evidence to support the hypothesis that WAP harvesting was associated with either poverty, or markers of HIV and/or AIDS affliction. Our findings suggest that generalisations about a possible interaction between HIV and/or AIDS and the environment may not uniformly apply to all categories of natural resources or to all user groups.
- Full Text:
- Authors: Kaschula, Sarah , Shackleton, Charlie M
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182344 , vital:43822 , xlink:href="https://hdl.handle.net/10520/EJC97203"
- Description: As a result of heightened financial and food insecurity, populations adversely affected by HIV and/or AIDS may be more likely to utilise wild natural resources to supplement their diet and livelihoods. Should this effect be pronounced, HIV and AIDS may pose a serious environmental threat. We explored the hypothesis that the presence of factors in the household, such as chronic illness in and recent mortality of individuals in a high HIV-risk age group, as well as the fostering of orphans, are associated with increased utilisation of wild animal products (WAPs) at the household level. We randomly surveyed 519 households from four sites in rural South Africa, recording household socio-economic status, the utilisation of wild animal products and health and demographic factors attributed to HIV or AIDS. Binary logistic regressions were used to test if households with markers of HIV and/or AIDS affliction were more likely to have a higher incidence and frequency of WAP utilisation relative to non-afflicted households, after adjusting for socio-economic and demographic variables. We found that, although households with markers of HIV and/or AIDS were generally poorer and had higher dependency ratios, there was no evidence to support the hypothesis that WAP harvesting was associated with either poverty, or markers of HIV and/or AIDS affliction. Our findings suggest that generalisations about a possible interaction between HIV and/or AIDS and the environment may not uniformly apply to all categories of natural resources or to all user groups.
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Imidazole-functionalized polymer microspheres and fibers–useful materials for immobilization of oxovanadium (IV) catalysts
- Walmsley, Ryan S, Ogunlaja, Adeniyi S, Coombes, Matthew J, Chidawanyika, Wadzanai J U, Litwinski, Christian, Torto, Nelson, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Walmsley, Ryan S , Ogunlaja, Adeniyi S , Coombes, Matthew J , Chidawanyika, Wadzanai J U , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246041 , vital:51431 , xlink:href="https://doi.org/10.1039/C2JM15485D"
- Description: Both polymer microspheres and microfibers containing the imidazole functionality have been prepared and used to immobilize oxovanadium(IV). The average diameters and BET surface areas of the microspheres were 322 μm and 155 m2 g−1 while the fibers were 1.85 μm and 52 m2 g−1, respectively. XPS and microanalysis confirmed the incorporation of imidazole and vanadium in the polymeric materials. The catalytic activity of both materials was evaluated using the hydrogen peroxide facilitated oxidation of thioanisole. The microspheres were applied in a typical laboratory batch reactor set-up and quantitative conversions (>99%) were obtained in under 240 min with turn-over frequencies ranging from 21.89 to 265.53 h−1, depending on the quantity of catalyst and temperature. The microspherical catalysts also proved to be recyclable with no drop in activity being observed after three successive reactions. The vanadium functionalized fibers were applied in a pseudo continuous flow set-up. Factors influencing the overall conversion and product selectivity, including flow rate and catalyst quantity, were investigated. At flow rates of 1–4 mL h−1 near quantitative conversion was maintained over an extended period. Keeping the mass of catalyst constant (0.025 g) and varying the flow rate from 1–6 mL h−1 resulted in a shift in the formation of the oxidation product methyl phenyl sulfone from 60.1 to 18.6%.
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- Authors: Walmsley, Ryan S , Ogunlaja, Adeniyi S , Coombes, Matthew J , Chidawanyika, Wadzanai J U , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246041 , vital:51431 , xlink:href="https://doi.org/10.1039/C2JM15485D"
- Description: Both polymer microspheres and microfibers containing the imidazole functionality have been prepared and used to immobilize oxovanadium(IV). The average diameters and BET surface areas of the microspheres were 322 μm and 155 m2 g−1 while the fibers were 1.85 μm and 52 m2 g−1, respectively. XPS and microanalysis confirmed the incorporation of imidazole and vanadium in the polymeric materials. The catalytic activity of both materials was evaluated using the hydrogen peroxide facilitated oxidation of thioanisole. The microspheres were applied in a typical laboratory batch reactor set-up and quantitative conversions (>99%) were obtained in under 240 min with turn-over frequencies ranging from 21.89 to 265.53 h−1, depending on the quantity of catalyst and temperature. The microspherical catalysts also proved to be recyclable with no drop in activity being observed after three successive reactions. The vanadium functionalized fibers were applied in a pseudo continuous flow set-up. Factors influencing the overall conversion and product selectivity, including flow rate and catalyst quantity, were investigated. At flow rates of 1–4 mL h−1 near quantitative conversion was maintained over an extended period. Keeping the mass of catalyst constant (0.025 g) and varying the flow rate from 1–6 mL h−1 resulted in a shift in the formation of the oxidation product methyl phenyl sulfone from 60.1 to 18.6%.
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Molecular catalysis of the oxygen reduction reaction by iron porphyrin catalysts tethered into Nafion layers
- He, Qinggang, Mugadza, Tawanda, Kang, Xiongwu, Zhu, Xiaobing, Chen, Shaowei, Kerr, John, Nyokong, Tebello
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
- Full Text:
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
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Physico-chemical properties of lutetium phthalocyanine complexes in solution and in solid polystyrene polymer fibers and their application in photoconversion of 4-nitrophenol
- Zugle, Ruphino, Nyokong, Tebello
- Authors: Zugle, Ruphino , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243520 , vital:51160 , xlink:href="https://doi.org/10.1016/j.molcata.2012.02.010"
- Description: The photophysical and photochemical behavior of two phthalocyanine complexes of lutetium peripherally substituted with tetraphenoxy and tetra-2-pyridiloxy groups were studied in solution and when dispersed in polystyrene polymer fiber. The phthalocyanines were found not to fluoresce significantly in solution and not at all within the fiber matrix as compared with standard unsubstituted zinc phthalocyanine. They showed very promising photoactivity in solution with high singlet oxygen quantum yields. Their photoactivity within the polymer fiber matrix was also demonstrated with the photoconversion of 4-nitrophenol, a water pollutant. The photodegradation process with both phthalocyanines follows first order kinetics similar to that observed for the zinc phthalocyanine and the photo-products were found to be hydroquinone, benzoquinone and 4-nitrocatechol.
- Full Text:
- Authors: Zugle, Ruphino , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243520 , vital:51160 , xlink:href="https://doi.org/10.1016/j.molcata.2012.02.010"
- Description: The photophysical and photochemical behavior of two phthalocyanine complexes of lutetium peripherally substituted with tetraphenoxy and tetra-2-pyridiloxy groups were studied in solution and when dispersed in polystyrene polymer fiber. The phthalocyanines were found not to fluoresce significantly in solution and not at all within the fiber matrix as compared with standard unsubstituted zinc phthalocyanine. They showed very promising photoactivity in solution with high singlet oxygen quantum yields. Their photoactivity within the polymer fiber matrix was also demonstrated with the photoconversion of 4-nitrophenol, a water pollutant. The photodegradation process with both phthalocyanines follows first order kinetics similar to that observed for the zinc phthalocyanine and the photo-products were found to be hydroquinone, benzoquinone and 4-nitrocatechol.
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Reverse saturation absorption spectra and optical limiting properties of chlorinated tetrasubstituted phthalocyanines containing different metals
- Tuhl, Ahmad, Manaa, Hacene, Makhseed, Saad, Al-Awadi, Nouria, Matthew, Jacob, Ibrahim, Hamada Mohamed, Nyokong, Tebello, Behbehani, Haider
- Authors: Tuhl, Ahmad , Manaa, Hacene , Makhseed, Saad , Al-Awadi, Nouria , Matthew, Jacob , Ibrahim, Hamada Mohamed , Nyokong, Tebello , Behbehani, Haider
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243498 , vital:51158 , xlink:href="https://doi.org/10.1016/j.optmat.2012.05.018"
- Description: A highly non-aggregated series of peripherally tetra(2,6-diisopropylphenoxy) substituted phthalocyanines (Pcs) containing different metals (Al, Ga, In and Zn) were prepared and their nonlinear optical properties (NLO), including the optical limiting behavior were investigated. This study explores the effect of the implanted metals along with the peripheral chlorine atoms on the NLO of the prepared complexes, thereby improving their optical limiting performance. The best wavelength at which the Pc complex exhibits the strongest nonlinear effect was determined over the low absorption window region (420–590 nm) comprised between the Q and B bands using a nanosecond pulsed laser with the aid of a Z-scan technique. The excited state absorption cross sections (σeff) have been found to be wavelength dependent with common double peaks at 505 nm and around 485 nm and the highest value was calculated for Pc1–In (1.1 × 10−16 cm2). The figure of merit spectra show different spectral structure when compared to the excited state absorption spectra and the largest figure of merit value was found to be around 107 for Pc1–In derivative. In full agreement with reverse saturation results, the optical limiting measurements, carried out at 485 nm and 532 nm for each derivative, show very low optical limiting thresholds at the former wavelength. In the continuous wave excitation regime, the Z-scan measurements, which were carried out at 632.8 and 532 nm, showed strong refractive and absorptive nonlinear effects.
- Full Text:
- Authors: Tuhl, Ahmad , Manaa, Hacene , Makhseed, Saad , Al-Awadi, Nouria , Matthew, Jacob , Ibrahim, Hamada Mohamed , Nyokong, Tebello , Behbehani, Haider
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243498 , vital:51158 , xlink:href="https://doi.org/10.1016/j.optmat.2012.05.018"
- Description: A highly non-aggregated series of peripherally tetra(2,6-diisopropylphenoxy) substituted phthalocyanines (Pcs) containing different metals (Al, Ga, In and Zn) were prepared and their nonlinear optical properties (NLO), including the optical limiting behavior were investigated. This study explores the effect of the implanted metals along with the peripheral chlorine atoms on the NLO of the prepared complexes, thereby improving their optical limiting performance. The best wavelength at which the Pc complex exhibits the strongest nonlinear effect was determined over the low absorption window region (420–590 nm) comprised between the Q and B bands using a nanosecond pulsed laser with the aid of a Z-scan technique. The excited state absorption cross sections (σeff) have been found to be wavelength dependent with common double peaks at 505 nm and around 485 nm and the highest value was calculated for Pc1–In (1.1 × 10−16 cm2). The figure of merit spectra show different spectral structure when compared to the excited state absorption spectra and the largest figure of merit value was found to be around 107 for Pc1–In derivative. In full agreement with reverse saturation results, the optical limiting measurements, carried out at 485 nm and 532 nm for each derivative, show very low optical limiting thresholds at the former wavelength. In the continuous wave excitation regime, the Z-scan measurements, which were carried out at 632.8 and 532 nm, showed strong refractive and absorptive nonlinear effects.
- Full Text:
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