Synthesis, photophysical and photochemical properties of octa-substituted antimony phthalocyanines
- Authors: Modibane, Desmond Kwena , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264226 , vital:53711 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.052"
- Description: This work reports on the synthesis and photophysicochemical parameters of unsubstituted [SbIIIPc]+I3- and octa-phenoxy ([SbIIIOPPc]+I3-) and -4-t-butylphenoxy ([SbIIIOTBPPc]+I3-) substituted antimony phthalocyanines. Photophysical and photochemical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide and toluene. The excitation spectra of oxidized antimony (Sb(V)Pc) derivates were similar to absorption spectra. Low fluorescence quantum yields, high triplet quantum yields and low triplet lifetimes were observed as the result of heavy atom (antimony ion).
- Full Text:
- Date Issued: 2009
Synthesis of phthalocyanine conjugates with gold nanoparticles and liposomes for photodynamic therapy
- Authors: Nombona, Nolwazi , Maduray, Kaminee , Antunes, Edith M , Karsten, Aletta , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245798 , vital:51406 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2011.11.007"
- Description: The efficiency of [2,9,17,23-tetrakis-(1,6-hexanedithiol)phthalocyaninato]zinc(II) as a photodynamic therapy (PDT) agent was investigated. This compound belongs to the second generation of photosensitizers currently tested for the cellular photo-damage of cancer cells. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizer were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either gold nanoparticles or encapsulated in liposomes. Cell viability studies showed the optimum phototoxic effect on non-malignant cells to be 4.5 J cm−2. The PDT effect of the liposome bound phthalocyanine showed extensive damage of the breast cancer cells. Gold nanoparticles only showed a modest improvement in PDT activity.
- Full Text:
- Date Issued: 2012
(Ferrocenylpyrazolyl) zinc (II) benzoates as catalysts for the ring opening polymerization of ε-caprolactone
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H L , Otto, Daniel P , Nyokong, Tebello , Darkwa, James
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189515 , vital:44853 , xlink:href="https://doi.org/10.1016/j.poly.2015.02.007"
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3 COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of e-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1 H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 107 h1 mol1 at 110 C.
- Full Text:
- Date Issued: 2015
A colorimetric probe for dopamine based on gold nanoparticles-electrospun nanofibre composite
- Authors: Ngomane, Nokuthula , Torto, Nelson , Krause, Rui W M , Vilakazi, Sibulelo
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195407 , vital:45562 , xlink:href="https://doi.org/10.1016/j.matpr.2015.08.036"
- Description: An easily prepared solid state colorimetric probe for detecting the neurotransmitter dopamine (DA) was developed. The probe, in the form of an electrospun Nylon−6 (N6) nanofibre with embedded un−functionalized gold nanoparticles (UF−AuNPs) produces a clear colour change in the presence of a DA that is detectable by the naked eye. Characterisation of the nanofibre using UV/vis spectroscopy and electron microscopy (TEM) confirmed the formation of the AuNPs in the polymer solution, and that the AuNPs were completely encapsulated within the composite nanofibres before exposure to the analytes. The probe exhibited very high sensitivity towards DA resulting in colour change of the composite fibres from purple to navy blue/black even under low concentrations of DA. The probe was also selective to DA since the colour remained unchanged in the presence of commonly encountered interfering species such as ascorbic acid, uric acid, catechol, epinephrine and norepinephrine. Moreover, the colour change was observed rapid, occurring either immediately on contact with higher concentrations (5 x10−4 M) or within about 3−5 min for the lower concentrations (e.g. 5 x10−7 M). Since this probe does not require the use of any instruments, and is both rapid and stable over time, it can be applied in the field by an inexperienced person.
- Full Text:
- Date Issued: 2015
A comparative photophysicochemical study of phthalocyanines encapsulated in core–shell silica nanoparticles
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189708 , vital:44924 , xlink:href="https://doi.org/10.1016/j.saa.2014.08.062"
- Description: This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4- carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix.
- Full Text:
- Date Issued: 2015
Comparative electrocatalytic studies of nanocomposites of mixed and covalently linked multiwalled carbon nanotubes and 4-(4, 6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt (II)
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189285 , vital:44834 , xlink:href="https://doi.org/10.1016/j.poly.2015.05.038"
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards L-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite.
- Full Text:
- Date Issued: 2015
Comparative photophysicochemical behavior of nanoconjugates of indium tetracarboxyphenoxy phthalocyanines covalently linked to CdTe/ZnSe/ZnO quantum dots
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7294 , http://hdl.handle.net/10962/d1020357 , http://dx.doi.org/10.1016/j.jphotochem.2015.07.009
- Description: This work reports on the photophysicochemical behavior of different nanoconjugates of core/shell/shell (GSH-CdTe/ZnSe/ZnO), core/shell (GSH-CdTe/ZnSe) and core (GSH-CdTe) (quantum dots QDs) with indium tetracarboxyphenoxy phthalocyanines ((OH)InTCPPc) in dimethylsulfoxide. The fluorescence quantum yields (Φf) and lifetimes (τf, in brackets) of QDs ranged from 0.20 (13.9 ns) to 0.42 (25.6 ns). The highest Φf value was obtained for GSH-CdTe/ZnSe/ZnO (4.5) while the least was observed in GSH-CdTe/ZnSe/ZnO (7.6), the numbers in brackets refer to the sizes. For (OH)InTCPPc alone a Φf and τf values of 0.02 and 2.43 ns, respectively were obtained. In the nanoconjugates, pivotal decrease in the Φf and τf of the QDs were observed with increase in the triplet and singlet oxygen quantum yields of (OH)InTCPPc. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2015.07.009
- Full Text: false
- Date Issued: 2015
Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- 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
Enhanced optical limiting behaviour of indium phthalocyanine derivatives when in solution or embedded in poly (acrylic acid) or poly (methyl methacrylate) polymers
- 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
- 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
- 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
- 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
- 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
- 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
Improved triplet state parameters for indium octacarboxy phthalocyanines when conjugated to quantum dots and magnetite nanoparticles
- 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
Local institutions, actors, and natural resource governance in Kgalagadi Transfrontier Park and surrounds, South Africa
- Authors: Thondhlana, Gladman , Shackleton, Sheona E , Blignaut, James
- Date: 2015
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/67689 , vital:29130 , https://doi.org/10.1016/j.landusepol.2015.03.013
- Description: Publisher version , Crafting local institutions to allow more effective decision-making in the management of and access to natural resources in and beyond parks has long been considered key to collaborative governance. South Africa, in particular, has vigorously pursued collaborative governance as a desired approach to managing natural resources as evident in the new arrangements for previously restricted parks. However, though the discourse of collaborative governance has occupied conservation thinking and practice globally, few studies have looked at the interplay between local institutions, actors and collaborative governance involving indigenous hunter–gatherer communities in Southern Africa. In response, we assess the local actors and institutions that were put in place to facilitate collaborative governance of natural resources in the Kgalagadi Transfrontier Park and its surrounds in South Africa. Our findings show that though collaborative governance has a practical appeal, it is hampered by lack of participation in decision-making, information dissemination, transparency, trust and accountability, power relations, divergent interests and unequal access to natural resources. The findings also draw our attention to issues of heterogeneity, even within indigenous communities assumed to be homogenous by local conservation authorities as reflected in land settlement agreements in co-managed parks. We argue that collaborative governance arrangements need to reflect and be understood within the broader background of complex local realities.
- Full Text: false
- Date Issued: 2015
Meso-and axially-modified IrIIItriarylcorroles with tunable electrocatalytic properties
- 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
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