Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes
- Mashazi, Philani N, Nyokong, Tebello
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
Electrode modification using alkynyl substituted Fe (II) phthalocyanine via electrografting and click chemistry for electrocatalysis
- Nxele, Siphesihle R, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189296 , vital:44835 , xlink:href="https://doi.org/10.1002/elan.201500212"
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM.
- Full Text:
- Date Issued: 2015
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189296 , vital:44835 , xlink:href="https://doi.org/10.1002/elan.201500212"
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM.
- Full Text:
- Date Issued: 2015
Enhanced optical limiting behaviour of indium phthalocyanine derivatives when in solution or embedded in poly (acrylic acid) or poly (methyl methacrylate) polymers
- Sanusi, Kayode, Nyokong, Tebello
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189445 , vital:44847 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.02.003"
- Description: The optical limiting performance of indium phthalocyanine-based polymer thin-films with large nonlinear absorption coefficients (βeff) and low limiting threshold intensity (Ilim) are described. The absorption cross-sections and the population dynamics of the excited states are also reported. The excited state absorption cross-sections (σexc) are shown to depend on the transition moment between the T1 and T2 states. βeff values have been shown to be related to the population density of the molecules in the T1 state. The improved optical limiting performance recorded for the investigated phthalocyanine complexes in the presence of polymer matrices has been attributed to the aggregation effects of the complexes in the polymer thin-films. The optical properties of the indium phthalocyanine moieties were found to possess robust sensitivity to a change of the polymer materials.
- Full Text:
- Date Issued: 2015
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189445 , vital:44847 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.02.003"
- Description: The optical limiting performance of indium phthalocyanine-based polymer thin-films with large nonlinear absorption coefficients (βeff) and low limiting threshold intensity (Ilim) are described. The absorption cross-sections and the population dynamics of the excited states are also reported. The excited state absorption cross-sections (σexc) are shown to depend on the transition moment between the T1 and T2 states. βeff values have been shown to be related to the population density of the molecules in the T1 state. The improved optical limiting performance recorded for the investigated phthalocyanine complexes in the presence of polymer matrices has been attributed to the aggregation effects of the complexes in the polymer thin-films. The optical properties of the indium phthalocyanine moieties were found to possess robust sensitivity to a change of the polymer materials.
- Full Text:
- Date Issued: 2015
Enhanced triplet state parameters for zinc carboxy phenoxy phthalocyanine following conjugation to ascorbic acid
- Ogbodu, Racheal O, Nyokong, Tebello
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189348 , vital:44839 , xlink:href="https://doi.org/10.1016/j.poly.2015.01.032"
- Description: Zinc phthalocyanine bearing four ascorbic acid units (formed via ester bond between zinc carboxy phenoxy phthalocyanines and ascorbic acid) was synthesized and characterized using different spectroscopic methods. The complex (with or without ascorbic acid) was further adsorbed onto single walled carbon nanotubes (SWCNTs) and further characterized using Raman spectroscopy, X-ray diffractometry, transmission electron microscopy and thermogravimetric analysis. The photophysical properties of the complexes were studied. The synthesized complex showed better photophysical properties when compared to the carboxy phenoxy phthalocyanines alone, this is evident in the increase of the triplet quantum yields (ΦT), triplet life-times (τT) and singlet oxygen quantum yields (ΦΔ). The zinc phthalocyanines bearing ascorbic acid showed improved triplet life-times even in the presence of SWCNTs.
- Full Text:
- Date Issued: 2015
- Authors: Ogbodu, Racheal O , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189348 , vital:44839 , xlink:href="https://doi.org/10.1016/j.poly.2015.01.032"
- Description: Zinc phthalocyanine bearing four ascorbic acid units (formed via ester bond between zinc carboxy phenoxy phthalocyanines and ascorbic acid) was synthesized and characterized using different spectroscopic methods. The complex (with or without ascorbic acid) was further adsorbed onto single walled carbon nanotubes (SWCNTs) and further characterized using Raman spectroscopy, X-ray diffractometry, transmission electron microscopy and thermogravimetric analysis. The photophysical properties of the complexes were studied. The synthesized complex showed better photophysical properties when compared to the carboxy phenoxy phthalocyanines alone, this is evident in the increase of the triplet quantum yields (ΦT), triplet life-times (τT) and singlet oxygen quantum yields (ΦΔ). The zinc phthalocyanines bearing ascorbic acid showed improved triplet life-times even in the presence of SWCNTs.
- Full Text:
- Date Issued: 2015
Enhanced triplet state yields in aqueous media of asymmetric zinc phthalocyanines when conjugated to silver nanoflowers
- D'Souza, Sarah, George, Reama, Göksel, Meltem, Atilla, Devrim, Durmus, Mahmut, Nyokong, Tebello
- Authors: D'Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmus, Mahmut , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189099 , vital:44816 , xlink:href="https://doi.org/10.1016/j.poly.2015.08.017"
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers.
- Full Text:
- Date Issued: 2015
- Authors: D'Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmus, Mahmut , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189099 , vital:44816 , xlink:href="https://doi.org/10.1016/j.poly.2015.08.017"
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers.
- Full Text:
- Date Issued: 2015
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Liang, Xu, Xu, Li, Li, Minzhi, Mack, John, Stone, Justin, Nyokong, Tebello, Jiang, Yu, Kobayashi, Nagao, Zhu, Weihua
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
Fluorescence behavior and singlet oxygen generating abilities of aluminum phthalocyanine in the presence of anisotropic gold nanoparticles
- Mthethwa, Thandekile, Nyokong, Tebello
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193598 , vital:45351 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193598 , vital:45351 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
Fluorescence behavior and singlet oxygen generating abilities of aluminum phthalocyanine in the presence of anisotropic gold nanoparticles
- Mthethwa, Thandekile, Nyokong, Tebello
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189865 , vital:44941 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189865 , vital:44941 , xlink:href="https://doi.org/10.1016/j.jlumin.2014.09.005"
- Description: Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs.
- Full Text:
- Date Issued: 2015
Fluorescence Behaviour of an Aluminium Octacarboxy Phthalocyanine-NaYGdF 4
- Taylor, Jessica, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
- Full Text:
- Date Issued: 2015
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
- Full Text:
- Date Issued: 2015
Food on the Table: Human Responses and Changing Coastal Fisheries in Solomon Islands
- Albert, Simon, Aswani, Shankar, Fisher, Paul L, Albert, Joelle
- Authors: Albert, Simon , Aswani, Shankar , Fisher, Paul L , Albert, Joelle
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/421887 , vital:71893 , xlink:href="https://doi.org/10.1371/journal.pone.0130800"
- Description: Globally the majority of commercial fisheries have experienced dramatic declines in stock and catch. Likewise, projections for many subsistence fisheries in the tropics indicate a dramatic decline is looming in the coming decades. In the Pacific Islands coastal fisheries provide basic subsistence needs for millions of people. A decline in fish catch would therefore have profound impacts on the health and livelihoods of these coastal communities. Given the decrease in local catch rates reported for many coastal communities in the Pacific, it is important to understand if fishers have responded to ecological change (either by expanding their fishing range and/or increasing their fishing effort), and if so, to evaluate the costs or benefits of these responses. We compare data from fish catches in 1995 and 2011 from a rural coastal community in Solomon Islands to examine the potentially changing coastal reef fishery at these time points. In particular we found changes in preferred fishing locations, fishing methodology and catch composition between these data sets. The results indicate that despite changes in catch rates (catch per unit effort) between data collected in 2011 and 16 years previously, the study community was able to increase gross catches through visiting fishing sites further away, diversifying fishing methods and targeting pelagic species through trolling. Such insight into local-scale responses to changing resources and/or fisheries development will help scientists and policy makers throughout the Pacific region in managing the region’s fisheries in the future.
- Full Text:
- Date Issued: 2015
- Authors: Albert, Simon , Aswani, Shankar , Fisher, Paul L , Albert, Joelle
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/421887 , vital:71893 , xlink:href="https://doi.org/10.1371/journal.pone.0130800"
- Description: Globally the majority of commercial fisheries have experienced dramatic declines in stock and catch. Likewise, projections for many subsistence fisheries in the tropics indicate a dramatic decline is looming in the coming decades. In the Pacific Islands coastal fisheries provide basic subsistence needs for millions of people. A decline in fish catch would therefore have profound impacts on the health and livelihoods of these coastal communities. Given the decrease in local catch rates reported for many coastal communities in the Pacific, it is important to understand if fishers have responded to ecological change (either by expanding their fishing range and/or increasing their fishing effort), and if so, to evaluate the costs or benefits of these responses. We compare data from fish catches in 1995 and 2011 from a rural coastal community in Solomon Islands to examine the potentially changing coastal reef fishery at these time points. In particular we found changes in preferred fishing locations, fishing methodology and catch composition between these data sets. The results indicate that despite changes in catch rates (catch per unit effort) between data collected in 2011 and 16 years previously, the study community was able to increase gross catches through visiting fishing sites further away, diversifying fishing methods and targeting pelagic species through trolling. Such insight into local-scale responses to changing resources and/or fisheries development will help scientists and policy makers throughout the Pacific region in managing the region’s fisheries in the future.
- Full Text:
- Date Issued: 2015
Genetic and biological characterisation of a novel Plutella xylostella granulovirus, PlxyGV-SA
- Abdulkadir, Fatima, Knox, Caroline M, Marsberg, Tamryn, Hill, Martin P, Moore, Sean D
- Authors: Abdulkadir, Fatima , Knox, Caroline M , Marsberg, Tamryn , Hill, Martin P , Moore, Sean D
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/417971 , vital:71498 , xlink:href="https://doi.org/10.1007/s10526-015-9666-3"
- Description: Plutella xylostella granulovirus (PlxyGV) has been isolated from insect populations in many countries and is considered a potential biopesticide for sustainable control of P. xylostella (L.) (Lepidoptera: Plutellidae). Several PlxyGV isolates have been genetically characterised, and the full genome sequence of PlxyGV-Japan is available for comparison with novel isolates. A South African PlxyGV was recently recovered from an overcrowded laboratory P. xylostella colony and identified as a genetically distinct isolate by sequencing of the granulin gene and restriction endonuclease (REN) analysis of genomic DNA. In this report, PlxyGV-SA was further characterised by PCR amplification and sequencing of egt, lef-8 and lef-9 genes, and several amino acid substitutions were observed. The PstI REN profile of PlxyGV-SA was different from that of PlxyGV-Japan in terms of band size and number, thereby confirming its novel genetic identity. Surface dose bioassays showed that PlxyGV-SA is pathogenic to neonate but not late instar larvae at the same and higher virus doses, indicating that a biopesticide should be targeted at early larval stages in the field.
- Full Text:
- Date Issued: 2015
- Authors: Abdulkadir, Fatima , Knox, Caroline M , Marsberg, Tamryn , Hill, Martin P , Moore, Sean D
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/417971 , vital:71498 , xlink:href="https://doi.org/10.1007/s10526-015-9666-3"
- Description: Plutella xylostella granulovirus (PlxyGV) has been isolated from insect populations in many countries and is considered a potential biopesticide for sustainable control of P. xylostella (L.) (Lepidoptera: Plutellidae). Several PlxyGV isolates have been genetically characterised, and the full genome sequence of PlxyGV-Japan is available for comparison with novel isolates. A South African PlxyGV was recently recovered from an overcrowded laboratory P. xylostella colony and identified as a genetically distinct isolate by sequencing of the granulin gene and restriction endonuclease (REN) analysis of genomic DNA. In this report, PlxyGV-SA was further characterised by PCR amplification and sequencing of egt, lef-8 and lef-9 genes, and several amino acid substitutions were observed. The PstI REN profile of PlxyGV-SA was different from that of PlxyGV-Japan in terms of band size and number, thereby confirming its novel genetic identity. Surface dose bioassays showed that PlxyGV-SA is pathogenic to neonate but not late instar larvae at the same and higher virus doses, indicating that a biopesticide should be targeted at early larval stages in the field.
- Full Text:
- Date Issued: 2015
Host searching and oviposition behaviour of Agathis bishopi (Hymenoptera: Braconidae), a larval parasitoid of false codling moth, Thaumatotibia leucotreta (Lepidoptera: Tortricidae): a potential proxy indicator for fruit infestation
- Zimba, Kennedy J, Heshula, LU, Moore, Sean D, Hill, Martin P
- Authors: Zimba, Kennedy J , Heshula, LU , Moore, Sean D , Hill, Martin P
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/407019 , vital:70330 , xlink:href="https://hdl.handle.net/10520/EJC195073"
- Description: Agathis bishopi (Nixon) (Hymenoptera: Braconidae)is an arrhenotokous larval endoparasitoid of Thaumatotibia leucotreta (Meyrick) (Lepidoptera: Tortricidae) (Gendall 2007; Hofmeyr et al. 2015) commonly known as false codling moth (FCM), a major pest of citrus in South Africa (Moore et al. 2004; Malan et al. 2011). Under field conditions, A. bishopi was identified attacking more than 34% of FCM larvae in fruit, showing good biocontrol potential (Gendall 2007). Preference by A. bishopi for parasitising the early instars of its concealed host suggests that the parasitoid has strong natural host location ability (Sishuba 2003; Gendall 2007).
- Full Text:
- Date Issued: 2015
- Authors: Zimba, Kennedy J , Heshula, LU , Moore, Sean D , Hill, Martin P
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/407019 , vital:70330 , xlink:href="https://hdl.handle.net/10520/EJC195073"
- Description: Agathis bishopi (Nixon) (Hymenoptera: Braconidae)is an arrhenotokous larval endoparasitoid of Thaumatotibia leucotreta (Meyrick) (Lepidoptera: Tortricidae) (Gendall 2007; Hofmeyr et al. 2015) commonly known as false codling moth (FCM), a major pest of citrus in South Africa (Moore et al. 2004; Malan et al. 2011). Under field conditions, A. bishopi was identified attacking more than 34% of FCM larvae in fruit, showing good biocontrol potential (Gendall 2007). Preference by A. bishopi for parasitising the early instars of its concealed host suggests that the parasitoid has strong natural host location ability (Sishuba 2003; Gendall 2007).
- Full Text:
- Date Issued: 2015
Improved triplet state parameters for indium octacarboxy phthalocyanines when conjugated to quantum dots and magnetite nanoparticles
- Tshangana, Charmaine, Nyokong, Tebello
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189337 , vital:44838 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: Fe3O4 magnetic nanoparticles (MNPs) and glutathione (GSH) capped CdSe@ZnS quantum dots (QDs) were separately coordinated to indium octacarboxy phthalocyanine (InPc(COOH)8) to form ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The photophysical parameters (triplet state and fluorescence quantum yields and lifetimes) were determined for the conjugates. The triplet quantum yields increased from ΦT = 0.49 for InPc(COOH)8 alone to ΦT = 0.61 and 0.56 for InPc(COOH)8 in the conjugates: ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The lifetimes also became longer for the conjugates compared to Pc alone.
- Full Text:
- Date Issued: 2015
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189337 , vital:44838 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: Fe3O4 magnetic nanoparticles (MNPs) and glutathione (GSH) capped CdSe@ZnS quantum dots (QDs) were separately coordinated to indium octacarboxy phthalocyanine (InPc(COOH)8) to form ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The photophysical parameters (triplet state and fluorescence quantum yields and lifetimes) were determined for the conjugates. The triplet quantum yields increased from ΦT = 0.49 for InPc(COOH)8 alone to ΦT = 0.61 and 0.56 for InPc(COOH)8 in the conjugates: ClInPc(COOH)8–MNPs and ClInPc(COOH)8–GSH–CdSe@ZnS, respectively. The lifetimes also became longer for the conjugates compared to Pc alone.
- Full Text:
- Date Issued: 2015
Integrating local knowledge and forest surveys to assess Lantana camara impacts on indigenous species recruitment in Mazeppa Bay, South Africa
- Jevon, Tui, Shackleton, Charlie M
- Authors: Jevon, Tui , Shackleton, Charlie M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180843 , vital:43650 , xlink:href="https://doi.org/10.1007/s10745-015-9748-y"
- Description: Invasive alien species have variable impacts on peoples’ livelihoods, plant communities and species at the local scale. Local people often have deeper insights into and experiences of these impacts than can be measured by scientific surveys. Here we examine the impacts of Lantana camara on the recruitment of indigenous forest species, many of which are used by local people. We integrate findings from conversations with elderly respondents with standard ecological surveys. Both sources of information indicate that the increasing presence of Lantana suppresses the number and species richness of recruits of indigenous forest species, which may retard forest succession. Dense thickets of Lantana also restricted access to non-timber forest products and species of cultural significance. The origin and date of the Lantana introduction in the area was identified by respondents as the 1960s and it escaped into the wild in the early 1970s. These findings can be incorporated into locally based management considerations.
- Full Text:
- Date Issued: 2015
- Authors: Jevon, Tui , Shackleton, Charlie M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180843 , vital:43650 , xlink:href="https://doi.org/10.1007/s10745-015-9748-y"
- Description: Invasive alien species have variable impacts on peoples’ livelihoods, plant communities and species at the local scale. Local people often have deeper insights into and experiences of these impacts than can be measured by scientific surveys. Here we examine the impacts of Lantana camara on the recruitment of indigenous forest species, many of which are used by local people. We integrate findings from conversations with elderly respondents with standard ecological surveys. Both sources of information indicate that the increasing presence of Lantana suppresses the number and species richness of recruits of indigenous forest species, which may retard forest succession. Dense thickets of Lantana also restricted access to non-timber forest products and species of cultural significance. The origin and date of the Lantana introduction in the area was identified by respondents as the 1960s and it escaped into the wild in the early 1970s. These findings can be incorporated into locally based management considerations.
- Full Text:
- Date Issued: 2015
Iodine-Doped Cobalt Phthalocyanine Supported on Multiwalled Carbon Nanotubes for Electrocatalysis of Oxygen Reduction Reaction
- Nyoni, Stephen, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nyoni, Stephen , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189434 , vital:44846 , xlink:href="https://doi.org/10.1002/elan.201400499"
- Description: 4-(4,6-Diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) was iodine doped, and its electrocatalytic properties explored. Physical characterization techniques such as UV-vis, X-ray photoelectron, electron paramagnetic resonance and infra-red spectroscopy were used. Cyclic voltammetry, electrochemical impedance spectroscopy and rotating disk electrode were used for electrochemical characterization of electrodes modified with the prepared phthalocyanine and its nanocomposites. The electrocatalytic effect of a new iodine-doped cobalt phthalocyanine derivative supported on multiwalled carbon nanotubes was then investigated towards oxygen reduction reaction. The electrocatalytic activity of the iodine-doped cobalt phthalocyanine was found to be superior in terms of current over the undoped phthalocyanine nanocomposite.
- Full Text:
- Date Issued: 2015
- Authors: Nyoni, Stephen , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189434 , vital:44846 , xlink:href="https://doi.org/10.1002/elan.201400499"
- Description: 4-(4,6-Diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) was iodine doped, and its electrocatalytic properties explored. Physical characterization techniques such as UV-vis, X-ray photoelectron, electron paramagnetic resonance and infra-red spectroscopy were used. Cyclic voltammetry, electrochemical impedance spectroscopy and rotating disk electrode were used for electrochemical characterization of electrodes modified with the prepared phthalocyanine and its nanocomposites. The electrocatalytic effect of a new iodine-doped cobalt phthalocyanine derivative supported on multiwalled carbon nanotubes was then investigated towards oxygen reduction reaction. The electrocatalytic activity of the iodine-doped cobalt phthalocyanine was found to be superior in terms of current over the undoped phthalocyanine nanocomposite.
- Full Text:
- Date Issued: 2015
Local wood demand, land cover change and the state of Albany thicket on an urban commonage in the Eastern Cape, South Africa
- Stickler, M M, Shackleton, Charlie M
- Authors: Stickler, M M , Shackleton, Charlie M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/398343 , vital:69402 , xlink:href="https://doi.org/10.1007/s00267-014-0396-6"
- Description: Understanding the rates and causes of land-use change is crucial in identifying solutions, especially in sensitive landscapes and ecosystems, as well as in places undergoing rapid political, socioeconomic or ecological change. Despite considerable concern at the rate of transformation and degradation of the biodiversity-rich Albany Thicket biome in South Africa, most knowledge is gleaned from private commercial lands and state conservation areas. In comparison, there is limited work in communal areas where land uses include biomass extraction, especially for firewood and construction timber. We used aerial photographs to analyze land use and cover change in the high- and low-use zones of an urban commonage and an adjacent protected area over almost six decades, which included a major political transition. Field sampling was undertaken to characterize the current state of the vegetation and soils of the commonage and protected area and to determine the supply and demand for firewood and construction timber. Between the 1950s and 1980s, there was a clear increase in woody vegetation cover, which was reversed after the political transition in the mid-1990s. However, current woody plant standing stocks and sustainable annual production rates are well above current firewood demand, suggesting other probable causes for the decline in woody plant cover. The fragmentation of woody plant cover is paralleled by increases in grassy areas and bare ground, an increase in soil compaction, and decreases in soil moisture, carbon, and nutrients.
- Full Text:
- Date Issued: 2015
- Authors: Stickler, M M , Shackleton, Charlie M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/398343 , vital:69402 , xlink:href="https://doi.org/10.1007/s00267-014-0396-6"
- Description: Understanding the rates and causes of land-use change is crucial in identifying solutions, especially in sensitive landscapes and ecosystems, as well as in places undergoing rapid political, socioeconomic or ecological change. Despite considerable concern at the rate of transformation and degradation of the biodiversity-rich Albany Thicket biome in South Africa, most knowledge is gleaned from private commercial lands and state conservation areas. In comparison, there is limited work in communal areas where land uses include biomass extraction, especially for firewood and construction timber. We used aerial photographs to analyze land use and cover change in the high- and low-use zones of an urban commonage and an adjacent protected area over almost six decades, which included a major political transition. Field sampling was undertaken to characterize the current state of the vegetation and soils of the commonage and protected area and to determine the supply and demand for firewood and construction timber. Between the 1950s and 1980s, there was a clear increase in woody vegetation cover, which was reversed after the political transition in the mid-1990s. However, current woody plant standing stocks and sustainable annual production rates are well above current firewood demand, suggesting other probable causes for the decline in woody plant cover. The fragmentation of woody plant cover is paralleled by increases in grassy areas and bare ground, an increase in soil compaction, and decreases in soil moisture, carbon, and nutrients.
- Full Text:
- Date Issued: 2015
Meso-and axially-modified IrIIItriarylcorroles with tunable electrocatalytic properties
- Zhang, Xifeng, Wang, Yu, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Liang, Xu
- Authors: Zhang, Xifeng , Wang, Yu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190851 , vital:45034 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: The synthesis of three A2B type Ir(III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties and three A3 type IrIIItriphenylcorroles with differing pyridine axial ligands is reported, along with their structural characterization. An analysis of the structure-property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy and electrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type IrIIItriarylcorroles are highly efficient electrocatalyzed oxygen reduction reactions (ORRs) and that their reactivity can be modulated by modulating the electronic structure by changing the nature of the meso-substituent at the B-positions, and even axial pyridine ligands.
- Full Text:
- Date Issued: 2015
- Authors: Zhang, Xifeng , Wang, Yu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190851 , vital:45034 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: The synthesis of three A2B type Ir(III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties and three A3 type IrIIItriphenylcorroles with differing pyridine axial ligands is reported, along with their structural characterization. An analysis of the structure-property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy and electrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type IrIIItriarylcorroles are highly efficient electrocatalyzed oxygen reduction reactions (ORRs) and that their reactivity can be modulated by modulating the electronic structure by changing the nature of the meso-substituent at the B-positions, and even axial pyridine ligands.
- Full Text:
- Date Issued: 2015
Mitochondrial STAT3 and reactive oxygen species: a fulcrum of adipogenesis?
- Kramer, Adam H, Kadye, Rose, Houseman, Pascalene S, Prinsloo, Earl
- Authors: Kramer, Adam H , Kadye, Rose , Houseman, Pascalene S , Prinsloo, Earl
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431674 , vital:72795 , xlink:href="https://doi.org/10.1080/21623996.2015.1084084"
- Description: The balance between cellular lineages can be controlled by reactive oxygen species (ROS). Cellular differentiation into adipocytes is highly dependent on the production of ROS to initiate the process through activation of multiple interlinked factors that stimulate mitotic clonal expansion and cellular maturation. The signal transducer and activator of transcription family of signaling proteins have accepted roles in adipogenesis and associated lipogenesis. Non-canonical mitochondrial localization of STAT3 and other members of the STAT family however opens up new avenues for investigation of its role in the aforementioned processes. Following recent observations of differences in mitochondrially localized serine 727 phosphorylated STAT3 (mtSTAT3-pS727) in preadipocytes and adipocytes, here, we hypothesize and speculate further on the role of mitochondrial STAT3 in adipogenesis.
- Full Text:
- Date Issued: 2015
- Authors: Kramer, Adam H , Kadye, Rose , Houseman, Pascalene S , Prinsloo, Earl
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/431674 , vital:72795 , xlink:href="https://doi.org/10.1080/21623996.2015.1084084"
- Description: The balance between cellular lineages can be controlled by reactive oxygen species (ROS). Cellular differentiation into adipocytes is highly dependent on the production of ROS to initiate the process through activation of multiple interlinked factors that stimulate mitotic clonal expansion and cellular maturation. The signal transducer and activator of transcription family of signaling proteins have accepted roles in adipogenesis and associated lipogenesis. Non-canonical mitochondrial localization of STAT3 and other members of the STAT family however opens up new avenues for investigation of its role in the aforementioned processes. Following recent observations of differences in mitochondrially localized serine 727 phosphorylated STAT3 (mtSTAT3-pS727) in preadipocytes and adipocytes, here, we hypothesize and speculate further on the role of mitochondrial STAT3 in adipogenesis.
- Full Text:
- Date Issued: 2015
Modelling stock return volatility dynamics in selected African markets
- Authors: King, Daniel , Botha, Ferdi
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/396104 , vital:69150 , xlink:href=" https://doi.org/10.1016/j.econmod.2014.11.008"
- Description: This paper examines whether accounting for structural changes in the conditional variance process, through the use of Markov-switching models, improves estimates and forecasts of stock return volatility over those of the more conventional single-state (G)ARCH models, within and across selected African markets for the period 2002–2012. In the univariate portion of the paper, the performances of various Markov-switching models are tested against a single-state benchmark model through the use of in-sample goodness-of-fit and predictive ability measures. In the multivariate context, the single-state and Markov-switching models are comparatively assessed according to their usefulness in constructing optimal stock portfolios. Accounting for structural breaks in the conditional variance process, conventional GARCH effects remain important in capturing heteroscedasticity. However, those univariate models including a GARCH term perform comparatively poorly when used for forecasting purposes. In the multivariate study, the use of Markov-switching variance–covariance estimates improves risk-adjusted portfolio returns relative to portfolios constructed using the more conventional single-state models. While there is evidence that some Markov-switching models can provide better forecasts and higher risk-adjusted returns than those models which include GARCH effects, the inability of the simpler Markov-switching models to fully capture heteroscedasticity in the data remains problematic.
- Full Text:
- Date Issued: 2015
- Authors: King, Daniel , Botha, Ferdi
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/396104 , vital:69150 , xlink:href=" https://doi.org/10.1016/j.econmod.2014.11.008"
- Description: This paper examines whether accounting for structural changes in the conditional variance process, through the use of Markov-switching models, improves estimates and forecasts of stock return volatility over those of the more conventional single-state (G)ARCH models, within and across selected African markets for the period 2002–2012. In the univariate portion of the paper, the performances of various Markov-switching models are tested against a single-state benchmark model through the use of in-sample goodness-of-fit and predictive ability measures. In the multivariate context, the single-state and Markov-switching models are comparatively assessed according to their usefulness in constructing optimal stock portfolios. Accounting for structural breaks in the conditional variance process, conventional GARCH effects remain important in capturing heteroscedasticity. However, those univariate models including a GARCH term perform comparatively poorly when used for forecasting purposes. In the multivariate study, the use of Markov-switching variance–covariance estimates improves risk-adjusted portfolio returns relative to portfolios constructed using the more conventional single-state models. While there is evidence that some Markov-switching models can provide better forecasts and higher risk-adjusted returns than those models which include GARCH effects, the inability of the simpler Markov-switching models to fully capture heteroscedasticity in the data remains problematic.
- Full Text:
- Date Issued: 2015