Surface properties and electrocatalytic applications of metallophthalocyanines confined on electrode surfaces
- Authors: Akinbulu, Isaac Adebayo
- Date: 2011
- Subjects: Phthalocyanines Electrochemistry Electrocatalysis Pesticides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4365 , http://hdl.handle.net/10962/d1005030
- Description: New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.
- Full Text:
- Authors: Akinbulu, Isaac Adebayo
- Date: 2011
- Subjects: Phthalocyanines Electrochemistry Electrocatalysis Pesticides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4365 , http://hdl.handle.net/10962/d1005030
- Description: New cobalt (13, 16 19 and 22), manganese (14, 17, 20 and 23) and iron (15, 18, 21 and 24)phthalocyanine complexes were synthesized and characterized. The UV-Vis spectral properties of the complexes were typical of the nature of central metal and position of substituent on the Pc ligand. Their electrochemical behaviors were signatures of the central metals, with varying influences of the nature and position of substituents. Nanocomposite of complex 18 and single walled carbon nanotubes (SWCNTs) (SWCNT-18)was fabricated. Formation of this nano-composite was confirmed by infrared (IR)spectroscopy, X-ray diffraction (XRD) spectroscopy and transmission electron microscopy (TEM). Self-assembled monolayers (SAMs) of SWCNT-18, complexes 13-15, and 20 were electropolymerized on glassy carbon electrodes (GCE). Complex 14 was also electrodeposited on GCE. Surface properties of the SAMs were consistent with the molecular feature of the substituent and the nature of central metal in the adsorbed species, while those of the MnPc modified GCEs were dependent on point of substitution and number of substituent. The SAM-modified gold electrodes were used for the electrocatalytic oxidation of the carbamate insecticide, carbofuran. Amplification of the current signal of the insecticide, at more energetically feasible oxidation potentials, on the SAM-modified gold electrodes, relative to bare gold electrode,justified electrocatalysis. There was enhanced sensitivity (attributed to the presence of SWCNT) of the SWCNT-18-SAM-modified gold electrode towards carbofuran, relative to the signals observed on the other SAMs. Current response of the insecticide,bendiocarb, was also intensified, at more favorable oxidation potentials, on the MnPc (14 and 17) modified GCEs, relative to the response on bare GCE, substantiating electrocatalysis. Also, catalysis of the oxidation of the herbicide, bentazon, was observed on polymeric film of complex 20. The current response of the herbicide on this film was better than that observed on bare GCE. Electrocatalysis of the analytes, on the respective modified electrodes, occurred via closely related mechanisms.
- Full Text:
Syntheses and electrochemical characterization of new water soluble octaarylthiosubstituted manganese phthalocyanines
- Booysen, Irvin N, Matemadombo, Fungisai, Durmus, Mahmut, Nyokong, Tebello
- Authors: Booysen, Irvin N , Matemadombo, Fungisai , Durmus, Mahmut , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247614 , vital:51600 , xlink:href="https://doi.org/10.1016/j.dyepig.2010.09.012"
- Description: This paper reports on the synthesis and characterization of new manganese phthalocyanine (MnPc) complexes: 2,3-octakis-[(2-mercaptopyridine) phthalocyaninato] acetato manganese (III) (1) and its quaternized (hence water soluble) derivative: 2,3-octakis-{[(N-methyl-2-mercaptopyridine) phthalocyaninato] acetato manganese (III)} sulphate (2). The complexes were used to form self assembled monolayers (SAMs). Voltammetry proved that both of the SAMs are well packed, strongly passivating and act as selective and efficient barriers to ion permeability. Furthermore, surface coverage studies confirmed that the MPc macrocycles adsorb onto the gold electrode as monolayers. Both MPc SAMs were successfully used as electrochemical sensors of nitrite.
- Full Text:
- Authors: Booysen, Irvin N , Matemadombo, Fungisai , Durmus, Mahmut , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247614 , vital:51600 , xlink:href="https://doi.org/10.1016/j.dyepig.2010.09.012"
- Description: This paper reports on the synthesis and characterization of new manganese phthalocyanine (MnPc) complexes: 2,3-octakis-[(2-mercaptopyridine) phthalocyaninato] acetato manganese (III) (1) and its quaternized (hence water soluble) derivative: 2,3-octakis-{[(N-methyl-2-mercaptopyridine) phthalocyaninato] acetato manganese (III)} sulphate (2). The complexes were used to form self assembled monolayers (SAMs). Voltammetry proved that both of the SAMs are well packed, strongly passivating and act as selective and efficient barriers to ion permeability. Furthermore, surface coverage studies confirmed that the MPc macrocycles adsorb onto the gold electrode as monolayers. Both MPc SAMs were successfully used as electrochemical sensors of nitrite.
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Syntheses, electrochemical and spectroelectrochemical properties of novel ball-type and mononuclear Co (II) phthalocyanines substituted at the peripheral and non-peripheral positions with binaphthol groups
- Canlıca, Mevlüde, Booysen, Irvin Noel, Nyokong, Tebello
- Authors: Canlıca, Mevlüde , Booysen, Irvin Noel , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247837 , vital:51622 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.017"
- Description: Mononuclear cobalt phthalocyanine (CoPc) substituted at the non-peripheral 8 and peripheral positions 9 with 1,1′-binaphthyl-8,8′-diol and ball-type dinuclear Co2Pc2 substituted at the non-peripheral 10 and peripheral 11 positions with the same substituent are reported. The complexes with 1,1′-binaphthol-bridges were prepared from the corresponding phthalonitriles 4–7. The effects of the position of substituent on spectral, electrochemical and spectroelectrochemical properties of these complexes were also explored. The mononuclear complexes 8 and 9 exhibited one metal reduction, one ring reduction and one ring oxidation. The redox properties of the ball-type complexes 10 and 11 exhibited two reduction processes assigned to [(CoIPc−2)2]2−/[(CoIPc−3)2]4− (I), (CoIIPc−2)2/[(CoIPc−2)2]2− (II) and one oxidation process assigned to [(CoIIIPc−2)2]2+/CoIIPc−2)2 (III). The ball-type complexes are much easier to oxidize and more difficult to reduce than the corresponding monomers 8 and 9.
- Full Text:
- Authors: Canlıca, Mevlüde , Booysen, Irvin Noel , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247837 , vital:51622 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.017"
- Description: Mononuclear cobalt phthalocyanine (CoPc) substituted at the non-peripheral 8 and peripheral positions 9 with 1,1′-binaphthyl-8,8′-diol and ball-type dinuclear Co2Pc2 substituted at the non-peripheral 10 and peripheral 11 positions with the same substituent are reported. The complexes with 1,1′-binaphthol-bridges were prepared from the corresponding phthalonitriles 4–7. The effects of the position of substituent on spectral, electrochemical and spectroelectrochemical properties of these complexes were also explored. The mononuclear complexes 8 and 9 exhibited one metal reduction, one ring reduction and one ring oxidation. The redox properties of the ball-type complexes 10 and 11 exhibited two reduction processes assigned to [(CoIPc−2)2]2−/[(CoIPc−3)2]4− (I), (CoIIPc−2)2/[(CoIPc−2)2]2− (II) and one oxidation process assigned to [(CoIIIPc−2)2]2+/CoIIPc−2)2 (III). The ball-type complexes are much easier to oxidize and more difficult to reduce than the corresponding monomers 8 and 9.
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Synthesis and electrocatalytic behavior of cobalt (II)-tris (benzyl-mercapto)-monoaminophthalocyanine–single walled carbon nanotube nanorods
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247882 , vital:51626 , xlink:href="https://doi.org/10.1016/j.electacta.2010.11.016"
- Description: In this paper we report on synthesis and electrocatalytic behavior of cobalt (II)-tris(benzyl-mercapto)-monoaminophthalocyanine–single walled carbon nanotube nanorods towards the oxidation of amitrole. SWCNTs that were terminally functionalized with carboxylic acid groups were chemically linked to cobalt (II)-tris(benzyl-mercapto) monoaminophthalocyanine (CoMAPc) via an amide bond to form nanorods. UV–vis, FTIR, TEM, Raman and XRD spectroscopies were used in characterization of the nanorods (CoMAPc–SWCNT-linked), while cyclic voltammetry and chronoamperometry were used during the characterization of amitrole on the modified glassy carbon electrode. The linear dynamic range for the amitrole was from 1.0 × 10−6 M to 1.2 × 10−4 M, with a sensitivity of 6.76 A mol−1 L cm−2. The estimated limit of detection for amitrole was 0.10 μM, using the 3δ criterion. The catalytic rate constant was found to be 1.09 × 105 M−1 s−1.
- Full Text:
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247882 , vital:51626 , xlink:href="https://doi.org/10.1016/j.electacta.2010.11.016"
- Description: In this paper we report on synthesis and electrocatalytic behavior of cobalt (II)-tris(benzyl-mercapto)-monoaminophthalocyanine–single walled carbon nanotube nanorods towards the oxidation of amitrole. SWCNTs that were terminally functionalized with carboxylic acid groups were chemically linked to cobalt (II)-tris(benzyl-mercapto) monoaminophthalocyanine (CoMAPc) via an amide bond to form nanorods. UV–vis, FTIR, TEM, Raman and XRD spectroscopies were used in characterization of the nanorods (CoMAPc–SWCNT-linked), while cyclic voltammetry and chronoamperometry were used during the characterization of amitrole on the modified glassy carbon electrode. The linear dynamic range for the amitrole was from 1.0 × 10−6 M to 1.2 × 10−4 M, with a sensitivity of 6.76 A mol−1 L cm−2. The estimated limit of detection for amitrole was 0.10 μM, using the 3δ criterion. The catalytic rate constant was found to be 1.09 × 105 M−1 s−1.
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Synthesis and electrochemical behavior of novel peripherally and non-peripherally substituted ball-type cobalt phthalocyanine complexes
- Canlıca, Mevlüde, Booysen, Irvin Noel, Nyokong, Tebello
- Authors: Canlıca, Mevlüde , Booysen, Irvin Noel , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247848 , vital:51623 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.028"
- Description: The syntheses of new ball-type Co(II) phthalocyanines containing 4,4′-(9H-fluorene-9,9-diyl)diphenol substituents at non-peripheral (complex 6) and peripheral (complex 7) positions are presented. These complexes were characterized by UV–Vis, FT-IR, mass spectroscopy and electrochemical methods. Both complexes exhibit metal and ring based redox processes, typical of cobalt phthalocyanine complexes. For 6, the metal based reduction was observed at −0.46 V followed by a ring based reduction at −1.40 V. The metal oxidation for 6 was observed at +0.16 V and the ring based oxidation at +1.05 V. For 7, reductions are easier but the oxidations are more difficult. The metal based reduction for 7 was observed at −0.38 V followed by a ring based reduction at −1.03 V. The metal oxidation for 7 was observed at +0.20 V and the ring based oxidation at +1.35 V.
- Full Text:
- Authors: Canlıca, Mevlüde , Booysen, Irvin Noel , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247848 , vital:51623 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.028"
- Description: The syntheses of new ball-type Co(II) phthalocyanines containing 4,4′-(9H-fluorene-9,9-diyl)diphenol substituents at non-peripheral (complex 6) and peripheral (complex 7) positions are presented. These complexes were characterized by UV–Vis, FT-IR, mass spectroscopy and electrochemical methods. Both complexes exhibit metal and ring based redox processes, typical of cobalt phthalocyanine complexes. For 6, the metal based reduction was observed at −0.46 V followed by a ring based reduction at −1.40 V. The metal oxidation for 6 was observed at +0.16 V and the ring based oxidation at +1.05 V. For 7, reductions are easier but the oxidations are more difficult. The metal based reduction for 7 was observed at −0.38 V followed by a ring based reduction at −1.03 V. The metal oxidation for 7 was observed at +0.20 V and the ring based oxidation at +1.35 V.
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Synthesis and electrochemical properties of new tetra substituted cobalt phthalocyanine complexes, and their application in electrode modification for the electrocatalysis of l-cysteine
- Erdoğmuş, Ali, Booysen, Irvin Noel, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Booysen, Irvin Noel , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247893 , vital:51627 , xlink:href="https://doi.org/10.1016/j.synthmet.2010.11.028"
- Description: This study investigates the synthesis and characterization new peripherally (β) tetra-substituted 4-(2-mercaptoquinoline phthalocyaninato) Co(II) (CoPcSHQn, 3), and 4-(2-phenoxy-4-trifluoromethylpyridine phthalocyaninato) Co(II) (CoPcOHPy, 4). These complexes were characterized by elemental analysis, IR, mass and electronic spectroscopies and electrochemical methods. Both complexes show well resolved redox peaks attributed to both ring and metal based processes. Spectroelectrochemistry was used to confirm the assignments of the redox processes. For CoPcSHQn (3): CoIPc−2/CoIPc−3 (E1/2 = −1.25 V, I), CoIIPc−2/CoIPc−2 (E1/2 = −0.57 V, II), CoIIIPc−2/CoIIPc−2 (E1/2 = +0.45 V, IV) and an irreversible process at Ep = +1.05 V vs Ag|AgCl for CoIIIPc−1/CoIIIPc−2 (V). Redox couple III at E1/2 = −0.15 V was ascribed to aggregation. In the case of CoPcOHPy (4): CoIPc−2/CoIPc−3 (E1/2 = −1.13 V, I), CoIIPc−2/CoIPc−2 (E1/2 = −0.45 V, II), CoIIIPc−2/CoIIPc−2 at E1/2 = +0.21 V (IV), and CoIIIPc−1/CoIIIPc−2 (E1/2 = +1.01 V vs Ag|AgCl, V). Again III is associated with the aggregated species. Both complexes were electrodeposited on a glassy carbon electrode (GCE). For complex 3 self-assembled monolayers was also formed. The modified (CoPc-GCE) electrodes electrocatalytically detected L-cysteine at Ep = 0.62 V (3-GCE) and 0.59 V (4-GCE) vs Ag|AgCl.
- Full Text:
- Authors: Erdoğmuş, Ali , Booysen, Irvin Noel , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247893 , vital:51627 , xlink:href="https://doi.org/10.1016/j.synthmet.2010.11.028"
- Description: This study investigates the synthesis and characterization new peripherally (β) tetra-substituted 4-(2-mercaptoquinoline phthalocyaninato) Co(II) (CoPcSHQn, 3), and 4-(2-phenoxy-4-trifluoromethylpyridine phthalocyaninato) Co(II) (CoPcOHPy, 4). These complexes were characterized by elemental analysis, IR, mass and electronic spectroscopies and electrochemical methods. Both complexes show well resolved redox peaks attributed to both ring and metal based processes. Spectroelectrochemistry was used to confirm the assignments of the redox processes. For CoPcSHQn (3): CoIPc−2/CoIPc−3 (E1/2 = −1.25 V, I), CoIIPc−2/CoIPc−2 (E1/2 = −0.57 V, II), CoIIIPc−2/CoIIPc−2 (E1/2 = +0.45 V, IV) and an irreversible process at Ep = +1.05 V vs Ag|AgCl for CoIIIPc−1/CoIIIPc−2 (V). Redox couple III at E1/2 = −0.15 V was ascribed to aggregation. In the case of CoPcOHPy (4): CoIPc−2/CoIPc−3 (E1/2 = −1.13 V, I), CoIIPc−2/CoIPc−2 (E1/2 = −0.45 V, II), CoIIIPc−2/CoIIPc−2 at E1/2 = +0.21 V (IV), and CoIIIPc−1/CoIIIPc−2 (E1/2 = +1.01 V vs Ag|AgCl, V). Again III is associated with the aggregated species. Both complexes were electrodeposited on a glassy carbon electrode (GCE). For complex 3 self-assembled monolayers was also formed. The modified (CoPc-GCE) electrodes electrocatalytically detected L-cysteine at Ep = 0.62 V (3-GCE) and 0.59 V (4-GCE) vs Ag|AgCl.
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Synthesis and evaluation of novel HIV-1 enzyme inhibitors
- Olomola, Temitope Oloruntoba
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
- Full Text:
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
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Synthesis and photophysical behaviour of tantalum and titanium phthalocyanines in the presence of gold nanoparticles
- Chauke, Vongani P, Arslanoglu, Yasin, Nyokong, Tebello
- Authors: Chauke, Vongani P , Arslanoglu, Yasin , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247545 , vital:51593 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.04.020"
- Description: We report on the synthesis of 2,(3)- (peripheral) and 1,(4)- (non-peripheral) (2-mercaptopyridine)phthalocyanine complexes of titanium (IV) oxide (5 and 6 respectively), and tantalum (III) hydroxide (7, peripheral only), their photochemical and photophysical parameters and the photocatalytic oxidation of cyclohexene in the presence of gold nanoparticles (AuNPs). The singlet oxygen quantum yield values increased in the presence of AuNPs, for complexes 5 and 6. The percentage conversion values for cyclohexene using 5, 6 and 7 were 27%, 20% and 14%, respectively. These values increased considerably in the presence of AuNPs, except complex for 7. The products obtained include cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,2-cyclohexanediol. Low values of singlet oxygen quantum yields favour the formation of 1,2-cyclohexanediol.
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- Authors: Chauke, Vongani P , Arslanoglu, Yasin , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247545 , vital:51593 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.04.020"
- Description: We report on the synthesis of 2,(3)- (peripheral) and 1,(4)- (non-peripheral) (2-mercaptopyridine)phthalocyanine complexes of titanium (IV) oxide (5 and 6 respectively), and tantalum (III) hydroxide (7, peripheral only), their photochemical and photophysical parameters and the photocatalytic oxidation of cyclohexene in the presence of gold nanoparticles (AuNPs). The singlet oxygen quantum yield values increased in the presence of AuNPs, for complexes 5 and 6. The percentage conversion values for cyclohexene using 5, 6 and 7 were 27%, 20% and 14%, respectively. These values increased considerably in the presence of AuNPs, except complex for 7. The products obtained include cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,2-cyclohexanediol. Low values of singlet oxygen quantum yields favour the formation of 1,2-cyclohexanediol.
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Synthesis and photophysical properties of a novel zinc photosensitizer and its gold nanoparticle conjugate
- Moeno, Sharon, Antunes, Edith M, Nyokong, Tebello
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247100 , vital:51546 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.07.007"
- Description: The peripherally tetra substituted zinc phthalocyanine with 1,6-hexanedithiol as substituent (THdTZnPc, 3) was synthesized and is reported for the first time in this work. The potential of this zinc complex as a suitable photosensitizer for use in photodynamic therapy was determined through the investigation of the photophysical and photochemical properties. In this work complex 3 is attached to gold nanoparticles through the terminal thiol groups of the phthalocyanine resulting in a 3-AuNP conjugate whose photophysicochemical properties are investigated. Fluorescence lifetimes were determined using time correlated single photon counting and they show an increase in the abundance of the monomeric species (τ2) for the Pc in the 3-AuNP conjugate: ∼1 and 0.71 (with respective lifetimes 2.69 ns and 2.86 ns) compared to the free complex 3 with abundances of 0.12 and 0.13 (with respective lifetimes 3.36 ns and 3.28 ns) in DMSO and DMF, respectively.
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- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247100 , vital:51546 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.07.007"
- Description: The peripherally tetra substituted zinc phthalocyanine with 1,6-hexanedithiol as substituent (THdTZnPc, 3) was synthesized and is reported for the first time in this work. The potential of this zinc complex as a suitable photosensitizer for use in photodynamic therapy was determined through the investigation of the photophysical and photochemical properties. In this work complex 3 is attached to gold nanoparticles through the terminal thiol groups of the phthalocyanine resulting in a 3-AuNP conjugate whose photophysicochemical properties are investigated. Fluorescence lifetimes were determined using time correlated single photon counting and they show an increase in the abundance of the monomeric species (τ2) for the Pc in the 3-AuNP conjugate: ∼1 and 0.71 (with respective lifetimes 2.69 ns and 2.86 ns) compared to the free complex 3 with abundances of 0.12 and 0.13 (with respective lifetimes 3.36 ns and 3.28 ns) in DMSO and DMF, respectively.
- Full Text:
Synthesis and photophysical studies of CdTe quantum dot-monosubstituted zinc phthalocyanine conjugates
- D'Souza, Sarah, Antunes, Edith M, Nyokong, Tebello
- Authors: D'Souza, Sarah , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247825 , vital:51621 , xlink:href="https://doi.org/10.1016/j.ica.2010.12.027"
- Description: The linkage of unsymmetrically monosubstituted 4-aminophenoxy zinc phthalocyanine (ZnAPPc, 5) to CdTe quantum dots capped with mercaptopropionic acid (MPA), L-cysteine (L-cys) or thioglycolic acid (TGA) has been achieved using the coupling agents ethyl-N(3-dimethylaminopropyl) carbodiimide and N-hydroxy succinimide, which facilitate formation of an amide bond to form the QD–ZnAPPc-linked conjugate. The formation of the amide bond was confirmed using Raman and IR spectroscopies. Atomic force microscopy (AFM) and UV–Vis spectroscopy were used further to characterise the conjugate. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnAPPc in both the linked (QD–ZnAPPc-linked) and mixed (QD:ZnAPPc-mixed) conjugates. The linked L-cys and TGA QDs conjugates (QD–ZnAPPc-linked) gave the largest FRET efficiencies hence showing the advantages of covalent linking. Fluorescence quantum yields of QDs were decreased in QD:ZnAPPc-mixed and QD:ZnAPPc-linked.
- Full Text:
- Authors: D'Souza, Sarah , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247825 , vital:51621 , xlink:href="https://doi.org/10.1016/j.ica.2010.12.027"
- Description: The linkage of unsymmetrically monosubstituted 4-aminophenoxy zinc phthalocyanine (ZnAPPc, 5) to CdTe quantum dots capped with mercaptopropionic acid (MPA), L-cysteine (L-cys) or thioglycolic acid (TGA) has been achieved using the coupling agents ethyl-N(3-dimethylaminopropyl) carbodiimide and N-hydroxy succinimide, which facilitate formation of an amide bond to form the QD–ZnAPPc-linked conjugate. The formation of the amide bond was confirmed using Raman and IR spectroscopies. Atomic force microscopy (AFM) and UV–Vis spectroscopy were used further to characterise the conjugate. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnAPPc in both the linked (QD–ZnAPPc-linked) and mixed (QD:ZnAPPc-mixed) conjugates. The linked L-cys and TGA QDs conjugates (QD–ZnAPPc-linked) gave the largest FRET efficiencies hence showing the advantages of covalent linking. Fluorescence quantum yields of QDs were decreased in QD:ZnAPPc-mixed and QD:ZnAPPc-linked.
- Full Text:
Synthesis and photophysical studies of monocarboxy phthalocyanines containing quaternizable groups
- Arslanoğlu, Yasin, Nyokong, Tebello
- Authors: Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246992 , vital:51535 , xlink:href="https://doi.org/10.1016/j.poly.2011.08.009"
- Description: This work reports on the synthesis and photophysical properties of novel unsymmetrically substituted monocarboxy magnesium (MgPc, 3), aluminum (ClAlPc, 4) and unmetallated (H2Pc, 5) phthalocyanines. Magnesium phthalocyanine (3) was converted into water soluble quaternized derivative (QMgPc, 6) by reaction with methyl iodide. The synthesized phthalocyanines were characterized by IR, UV–Vis, NMR, mass spectrometry and elemental analyses. Photophysical and photochemical studies were carried out in order to determine the potential of the complexes as photosensitizers for use in photodynamic therapy. Triplet quantum yields ranged from 0.37 to 0.40 and triplet lifetimes from 110 to 140 μs in DMSO.
- Full Text:
- Authors: Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246992 , vital:51535 , xlink:href="https://doi.org/10.1016/j.poly.2011.08.009"
- Description: This work reports on the synthesis and photophysical properties of novel unsymmetrically substituted monocarboxy magnesium (MgPc, 3), aluminum (ClAlPc, 4) and unmetallated (H2Pc, 5) phthalocyanines. Magnesium phthalocyanine (3) was converted into water soluble quaternized derivative (QMgPc, 6) by reaction with methyl iodide. The synthesized phthalocyanines were characterized by IR, UV–Vis, NMR, mass spectrometry and elemental analyses. Photophysical and photochemical studies were carried out in order to determine the potential of the complexes as photosensitizers for use in photodynamic therapy. Triplet quantum yields ranged from 0.37 to 0.40 and triplet lifetimes from 110 to 140 μs in DMSO.
- Full Text:
Synthesis and photophysical studies of phthalocyanine–gold nanoparticle conjugates
- Nombona, Nolwazi, Antunes, Edith M, Litwinski, Christian, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
- Full Text:
- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
- Full Text:
Synthesis of novel inhibitors of 1-Deoxy-D-xylulose-5-phosphate reductoisomerase as potential anti-malarial lead compounds
- Authors: Mutorwa, Marius Kudumo
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Malaria -- Chemotherapy Drug development Lead compounds Phosphonates Phosphonic acids Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4372 , http://hdl.handle.net/10962/d1005037
- Description: This research has focused on the development of novel substrate mimics as potential DXR inhibitors of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), an essential enzyme in the mevalonate-independent pathway for the biosynthesis of isoprenoids in Plasmodium falciparum. DXR mediates the isomerisation and reduction of 1-deoxy-D-xylulose-5-phosphate (DOXP) into 2C-methyl-D-erithrytol 4-phosphate (MEP) and has been validated as an attractive target for the development of novel anti-malarial chemotherapeutic agents. Reaction of various amines with specially prepared 4-phosphonated crotonic acid in the presence of the peptide coupling reagent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), has afforded a series of amido-phosphonate esters in moderate to good yields (48% - 73%) which, using a RuCl₃/CeCl₃/NaIO₄ catalyst system, have been dihydroxylated to furnish the dihydroxy-amido phosphonate ester pro-drugs; subsequent hydrolysis under microwave irradiation has afforded the corresponding phosphonic acids. A second series of potential inhibitors viz., 3-substituted aniline-derived phosphonate esters, their corresponding phosphonic acids and mono-sodium salts, have also been successfully synthesised. In these compounds, the essential functional groups are separated by one, two, three or four methylene groups, Deprotonation of the 3-substituted aniline substrates, followed by reaction with the appropriate ω-chloroalkanoyl chloride produced the ω-chloroamide intermediates, which were subjected to the Michaelis-Arbuzov reaction to afford the diethyl phosphonate esters in moderate to good yields (48% - 74%). Microwave-assisted TMSBrmediated cleavage of the phosphonate esters furnished the phosphonic acids, neutralisation of which afforded the mono-sodium salts. Furan-derived phosphate esters and phosphonic acids have been prepared as conformationally-restricted DOXP analogues. Functionalization at C-5 of the trityl-protected furan was achieved using the Vilsmeier-Haack formylation and Friedel-Crafts acylation reactions and, following de-tritylation, phosphorylation and oximation, using hydroxylamine hydrochloride, the novel oxime derivatives have been isolated as a third series of potential DXR inhibitors in very good yields (87% - 96%). Finally, in order to exploit an additional binding pocket in the PƒDXR active site, a series of N-benzylated phosphoramidic derivatives were obtained in seven steps from the starting material, diethyl phosphoramidate. The known inhibitors, fosmidomycin and its acetyl derivative FR900098, were also successfully synthesised as standards for STD-NMR binding and inhibition assays. In all, over 200 compounds (136 novel) have been prepared and appropriately characterised using 1-and 2-D NMR and IR spectroscopic analysis and, where necessary, HRMS or combustion analysis. Saturation Transfer Difference (STD) protein-NMR experiments, undertaken using selected compounds, have revealed binding of most of the ligands examined to EcDXR. Computersimulated docking studies have also been used to explore the preferred ligand-binding conformations and interactions between the ligands and essential DXR active-site residues, while DXR-enzyme inhibition assays of selected synthesised ligands have revealed certain patterns of inhibitory activity.
- Full Text:
- Authors: Mutorwa, Marius Kudumo
- Date: 2011
- Subjects: Antimalarials -- Development Plasmodium falciparum Malaria -- Chemotherapy Drug development Lead compounds Phosphonates Phosphonic acids Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4372 , http://hdl.handle.net/10962/d1005037
- Description: This research has focused on the development of novel substrate mimics as potential DXR inhibitors of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), an essential enzyme in the mevalonate-independent pathway for the biosynthesis of isoprenoids in Plasmodium falciparum. DXR mediates the isomerisation and reduction of 1-deoxy-D-xylulose-5-phosphate (DOXP) into 2C-methyl-D-erithrytol 4-phosphate (MEP) and has been validated as an attractive target for the development of novel anti-malarial chemotherapeutic agents. Reaction of various amines with specially prepared 4-phosphonated crotonic acid in the presence of the peptide coupling reagent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), has afforded a series of amido-phosphonate esters in moderate to good yields (48% - 73%) which, using a RuCl₃/CeCl₃/NaIO₄ catalyst system, have been dihydroxylated to furnish the dihydroxy-amido phosphonate ester pro-drugs; subsequent hydrolysis under microwave irradiation has afforded the corresponding phosphonic acids. A second series of potential inhibitors viz., 3-substituted aniline-derived phosphonate esters, their corresponding phosphonic acids and mono-sodium salts, have also been successfully synthesised. In these compounds, the essential functional groups are separated by one, two, three or four methylene groups, Deprotonation of the 3-substituted aniline substrates, followed by reaction with the appropriate ω-chloroalkanoyl chloride produced the ω-chloroamide intermediates, which were subjected to the Michaelis-Arbuzov reaction to afford the diethyl phosphonate esters in moderate to good yields (48% - 74%). Microwave-assisted TMSBrmediated cleavage of the phosphonate esters furnished the phosphonic acids, neutralisation of which afforded the mono-sodium salts. Furan-derived phosphate esters and phosphonic acids have been prepared as conformationally-restricted DOXP analogues. Functionalization at C-5 of the trityl-protected furan was achieved using the Vilsmeier-Haack formylation and Friedel-Crafts acylation reactions and, following de-tritylation, phosphorylation and oximation, using hydroxylamine hydrochloride, the novel oxime derivatives have been isolated as a third series of potential DXR inhibitors in very good yields (87% - 96%). Finally, in order to exploit an additional binding pocket in the PƒDXR active site, a series of N-benzylated phosphoramidic derivatives were obtained in seven steps from the starting material, diethyl phosphoramidate. The known inhibitors, fosmidomycin and its acetyl derivative FR900098, were also successfully synthesised as standards for STD-NMR binding and inhibition assays. In all, over 200 compounds (136 novel) have been prepared and appropriately characterised using 1-and 2-D NMR and IR spectroscopic analysis and, where necessary, HRMS or combustion analysis. Saturation Transfer Difference (STD) protein-NMR experiments, undertaken using selected compounds, have revealed binding of most of the ligands examined to EcDXR. Computersimulated docking studies have also been used to explore the preferred ligand-binding conformations and interactions between the ligands and essential DXR active-site residues, while DXR-enzyme inhibition assays of selected synthesised ligands have revealed certain patterns of inhibitory activity.
- Full Text:
Synthesis, characterization and application of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in electrocatalysis
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247399 , vital:51577 , xlink:href="https://doi.org/10.1016/j.poly.2011.04.020"
- Description: In this paper we report on the synthesis, characterization and use of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in the electrocatalysis of amitrole and diuron. UV–Vis, FTIR and XRD spectroscopies were used in the characterization of cobalt(II)-tris(benzyl-mercapto)-mono(carboxyphenoxy)-phthalocyanine conjugates (CoMCPc–PA-SWCNT(linked)), while AFM was used to show changes in surface morphologies of the modified electrodes. Cyclic voltammetry and chronoamperometry were used for the electrocatalytic oxidation of amitrole and diuron on the modified glassy carbon electrode. The catalytic rate constants for amitrole and diuron were found to be 1.83 × 106 and 1.99 × 106 M−1 s−1, respectively. The linear range for both was 1.0 × 10−5–2.0 × 10−4 M, with sensitivities of 5.10 and 3.70 A mol−1 L cm−2 for amitrole and diuron, respectively. The limits of detection were estimated to be 0.14 and 0.20 μM for amitrole and diuron, respectively, using the 3δ notation.
- Full Text:
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247399 , vital:51577 , xlink:href="https://doi.org/10.1016/j.poly.2011.04.020"
- Description: In this paper we report on the synthesis, characterization and use of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in the electrocatalysis of amitrole and diuron. UV–Vis, FTIR and XRD spectroscopies were used in the characterization of cobalt(II)-tris(benzyl-mercapto)-mono(carboxyphenoxy)-phthalocyanine conjugates (CoMCPc–PA-SWCNT(linked)), while AFM was used to show changes in surface morphologies of the modified electrodes. Cyclic voltammetry and chronoamperometry were used for the electrocatalytic oxidation of amitrole and diuron on the modified glassy carbon electrode. The catalytic rate constants for amitrole and diuron were found to be 1.83 × 106 and 1.99 × 106 M−1 s−1, respectively. The linear range for both was 1.0 × 10−5–2.0 × 10−4 M, with sensitivities of 5.10 and 3.70 A mol−1 L cm−2 for amitrole and diuron, respectively. The limits of detection were estimated to be 0.14 and 0.20 μM for amitrole and diuron, respectively, using the 3δ notation.
- Full Text:
Synthesis, characterization, and photophysical properties of novel ball-type dinuclear and mononuclear containing four 1, 1′-binaphthyl-8, 8′-diol bridged metallophthalocyanines with long triplet state lifetimes
- Canlıca, Mevlude, Nyokong, Tebello
- Authors: Canlıca, Mevlude , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248406 , vital:51683 , xlink:href="https://doi.org/10.1039/C0DT01749C"
- Description: The syntheses of new ball-type dinuclear Si(IV)(CH3COO)2 and Ti(IV)O phthalocyanines and two different mononuclear Zn(II) and Ti(IV)O phthalocyanines containing four 1,1′-binaphthyl-8,8′-diol substituents on the peripheral positions are described. The structures of these compounds were characterized using the elemental analyzes, UV-Vis, FT-IR, 1H NMR and mass spectroscopies. The ΦF values are 0.14, 0.10, 0.04, 0.02, 0.07; ΦT values are 0.69, 0.71, 0.85, 0.33, 0.71 for 7–11, respectively. All complexes showed very long triplet lifetimes with τT 7510, 3190, 2880, 2370, 9470 μs for 7–11 in DMSO, respectively.
- Full Text:
- Authors: Canlıca, Mevlude , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248406 , vital:51683 , xlink:href="https://doi.org/10.1039/C0DT01749C"
- Description: The syntheses of new ball-type dinuclear Si(IV)(CH3COO)2 and Ti(IV)O phthalocyanines and two different mononuclear Zn(II) and Ti(IV)O phthalocyanines containing four 1,1′-binaphthyl-8,8′-diol substituents on the peripheral positions are described. The structures of these compounds were characterized using the elemental analyzes, UV-Vis, FT-IR, 1H NMR and mass spectroscopies. The ΦF values are 0.14, 0.10, 0.04, 0.02, 0.07; ΦT values are 0.69, 0.71, 0.85, 0.33, 0.71 for 7–11, respectively. All complexes showed very long triplet lifetimes with τT 7510, 3190, 2880, 2370, 9470 μs for 7–11 in DMSO, respectively.
- Full Text:
Systematics, morphology, phylogeny and historical biogeography of the Mayfly family Prosopistomatidae (Ephemeroptera: Insecta) of the world
- Barber-James, Helen Margaret
- Authors: Barber-James, Helen Margaret
- Date: 2011
- Subjects: Mayflies Mayflies -- Classification Mayflies -- Morphology Mayflies -- Phylogeny Mayflies -- Geographical distribution Ephemeridae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5785 , http://hdl.handle.net/10962/d1005473
- Description: The diversity, classification and historical biogeography of the mayfly family Prosopistomatidae are explored. First, the higher classification of the Ephemeroptera is reviewed, focussing on the phylogenetic placement of the Prosopistomatidae relative to other mayfly families. All relevant literature from 1762 to 2010 is synthesized. Baetiscidae are established as the probable sister lineage of Prosopistomatidae, the two constituting the superfamily Baetiscoidea. Next, qualitative morphological variation within the Prosopistomatidae is reviewed and revised, emphasizing nymphs because imaginal specimens are few. The labium and associated structures and the hypopharynx of nymphs, and the highly-derived wing venation of the imaginal stages, are re-interpreted. The structure of the male tarsal claws changes considerably between subimago and imago, which, together with deeply scalloped ridges on male imaginal forelegs and unusual pits on the female thorax, are interpreted as providing an unusual mating mechanism. These structures provide morphological characters for species definition and phylogenetic analyses. Two approaches to species delimitation are explored. First, morphometric variation is analysed using Principal Component Analysis, revealing groupings that can be interpreted as species, although there is some overlap between them. Discriminant Function Analysis shows that head width and carapace shape have the most value in identifying nymphs of different species. The carapace of Prosopistoma nymphs is shown to grow allometrically and gradually, in contrast with that of Baetisca, indicating a difference in early ontogeny. Second, an Artificial Neural Network algorithm applied to nymphal morphological characters accurately identified species. This computer-driven artificial intelligence method has power to provide future easy-to-use electronic identification aids. Phylogenetic analysis of nymphal morphology using the parsimony method shows two clades of Prosopistomatidae, one sharing characters with the type species, Prosopistoma variegatum and the other predominating in Africa, although also occurring in Asia; these clades are named the “P. variegatum” and “African” clades, respectively. Parsimony analysis of adult morphology supports these two clades, but supertree analysis obscures the relationships, nesting the “P. variegatum” lineage within the other clade. Preliminary molecular phylogenetic analysis of the 16S rRNA, (mitochondrial) 18S rRNA and Histone-3 genes using Bayesian Inference methods does not support the two clades shown by morphology. Instead, there is a strong relationship between the European species and one African species, with the single Asian representative being most distantly related. These results are limited by lack of fresh material, patchy taxon sampling, and problems with finding suitable primers. A molecular clock program, BEAST, calibrated using fossils, suggests divergence times for the oldest crown-group Prosopistoma clade, represented by the Asian P. wouterae, of about 131 Ma, with the youngest species, the African P. crassi, of 1.21 Ma. Stem-group relationships are analysed using parsimony analysis, focussing on wing characters of the Baetiscoidea, other extant mayfly lineages, and extinct stem-group lineages. This suggests that the Baetiscoidea diverged from main-line Ephemeroptera earlier than any other extant mayfly lineage. This approach expands upon ideas hinted at by earlier scientists. Finally, historical biogeographical analysis of the distribution of known Baetiscoidea s.s. stem-group fossils implies a once Pangean distribution of the lineage. Changing palaeo-climate, catastrophic extinction events and plate tectonic movements in relation to the distribution of crown-group species are reviewed. Other approaches to historical biogeography that build on both morphological and molecular phylogenies are used to interpret disperalist and vacarianist arguments. Distribution patterns of eight unrelated freshwater organisms which share a similar distribution pattern are compared, assuming that shared patterns indicate similar historic biogeographic processes. The distribution of recent Prosopistoma species is seen to be the product of evolution resulting from both vicariance and dispersal. In conclusion, this thesis encompasses a variety of disciplines. It successfully recognises new characters and distinguishes previously unknown species. It uses new approaches to delimiting species and known methods to determine phylogeny from several angles. The analysis of stem-group relationships offers an insight into possible early lineage splitting within Ephemeroptera. Interpretation of historical biogeography allows for both a Gondwanan origin of Prosopistomatidae, with rafting of species on the Deccan plate to Asia, and for subsequent dispersal from Asia down to Australia and across to Europe, and possibly back to Africa.
- Full Text:
- Authors: Barber-James, Helen Margaret
- Date: 2011
- Subjects: Mayflies Mayflies -- Classification Mayflies -- Morphology Mayflies -- Phylogeny Mayflies -- Geographical distribution Ephemeridae
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5785 , http://hdl.handle.net/10962/d1005473
- Description: The diversity, classification and historical biogeography of the mayfly family Prosopistomatidae are explored. First, the higher classification of the Ephemeroptera is reviewed, focussing on the phylogenetic placement of the Prosopistomatidae relative to other mayfly families. All relevant literature from 1762 to 2010 is synthesized. Baetiscidae are established as the probable sister lineage of Prosopistomatidae, the two constituting the superfamily Baetiscoidea. Next, qualitative morphological variation within the Prosopistomatidae is reviewed and revised, emphasizing nymphs because imaginal specimens are few. The labium and associated structures and the hypopharynx of nymphs, and the highly-derived wing venation of the imaginal stages, are re-interpreted. The structure of the male tarsal claws changes considerably between subimago and imago, which, together with deeply scalloped ridges on male imaginal forelegs and unusual pits on the female thorax, are interpreted as providing an unusual mating mechanism. These structures provide morphological characters for species definition and phylogenetic analyses. Two approaches to species delimitation are explored. First, morphometric variation is analysed using Principal Component Analysis, revealing groupings that can be interpreted as species, although there is some overlap between them. Discriminant Function Analysis shows that head width and carapace shape have the most value in identifying nymphs of different species. The carapace of Prosopistoma nymphs is shown to grow allometrically and gradually, in contrast with that of Baetisca, indicating a difference in early ontogeny. Second, an Artificial Neural Network algorithm applied to nymphal morphological characters accurately identified species. This computer-driven artificial intelligence method has power to provide future easy-to-use electronic identification aids. Phylogenetic analysis of nymphal morphology using the parsimony method shows two clades of Prosopistomatidae, one sharing characters with the type species, Prosopistoma variegatum and the other predominating in Africa, although also occurring in Asia; these clades are named the “P. variegatum” and “African” clades, respectively. Parsimony analysis of adult morphology supports these two clades, but supertree analysis obscures the relationships, nesting the “P. variegatum” lineage within the other clade. Preliminary molecular phylogenetic analysis of the 16S rRNA, (mitochondrial) 18S rRNA and Histone-3 genes using Bayesian Inference methods does not support the two clades shown by morphology. Instead, there is a strong relationship between the European species and one African species, with the single Asian representative being most distantly related. These results are limited by lack of fresh material, patchy taxon sampling, and problems with finding suitable primers. A molecular clock program, BEAST, calibrated using fossils, suggests divergence times for the oldest crown-group Prosopistoma clade, represented by the Asian P. wouterae, of about 131 Ma, with the youngest species, the African P. crassi, of 1.21 Ma. Stem-group relationships are analysed using parsimony analysis, focussing on wing characters of the Baetiscoidea, other extant mayfly lineages, and extinct stem-group lineages. This suggests that the Baetiscoidea diverged from main-line Ephemeroptera earlier than any other extant mayfly lineage. This approach expands upon ideas hinted at by earlier scientists. Finally, historical biogeographical analysis of the distribution of known Baetiscoidea s.s. stem-group fossils implies a once Pangean distribution of the lineage. Changing palaeo-climate, catastrophic extinction events and plate tectonic movements in relation to the distribution of crown-group species are reviewed. Other approaches to historical biogeography that build on both morphological and molecular phylogenies are used to interpret disperalist and vacarianist arguments. Distribution patterns of eight unrelated freshwater organisms which share a similar distribution pattern are compared, assuming that shared patterns indicate similar historic biogeographic processes. The distribution of recent Prosopistoma species is seen to be the product of evolution resulting from both vicariance and dispersal. In conclusion, this thesis encompasses a variety of disciplines. It successfully recognises new characters and distinguishes previously unknown species. It uses new approaches to delimiting species and known methods to determine phylogeny from several angles. The analysis of stem-group relationships offers an insight into possible early lineage splitting within Ephemeroptera. Interpretation of historical biogeography allows for both a Gondwanan origin of Prosopistomatidae, with rafting of species on the Deccan plate to Asia, and for subsequent dispersal from Asia down to Australia and across to Europe, and possibly back to Africa.
- Full Text:
Tartarus: A honeypot based malware tracking and mitigation framework
- Hunter, Samuel O, Irwin, Barry V W
- Authors: Hunter, Samuel O , Irwin, Barry V W
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/428629 , vital:72525 , https://d1wqtxts1xzle7.cloudfront.net/96055420/Hunter-libre.pdf?1671479103=andresponse-content-disposi-tion=inline%3B+filename%3DTartarus_A_honeypot_based_malware_tracki.pdfandExpires=1714722666andSignature=JtPpR-IoAXILqsIJSlmCEvn6yyytE17YLQBeFJRKD5aBug-EbLxFpEGDf4GtQXHbxHvR4~E-b5QtMs1H6ruSYDti9fIHenRbLeepZTx9jYj92to3qZjy7UloigYbQuw0Y6sN95jI7d4HX-Xkspbz0~DsnzwFmLGopg7j9RZSHqpSpI~fBvlml3QQ2rLCm4aB9u8tSW8du5u~FiJgiLHNgJaPzEOzy4~yfKkXBh--LTFdgeAVYxQbOESGGh9k5bc-LDJhQ6dD5HpXsM3wKJvYuVyU6m83vT2scogVgKHIr-t~XuiqL35PfI3hs2c~ZO0TH4hCqwiNMHQ8GCYsLvllsA__andKey-Pair-Id=APKAJLOHF5GGSLRBV4ZA
- Description: On a daily basis many of the hosts connected to the Internet experi-ence continuous probing and attack from malicious entities. Detection and defence from these malicious entities has primarily been the con-cern of Intrusion Detection Systems, Intrusion Prevention Systems and Anti-Virus software. These systems rely heavily on known signatures to detect nefarious traffic. Due to the reliance on known malicious signa-tures, these systems have been at a serious disadvantage when it comes to detecting new, never before seen malware. This paper will introduce Tartarus which is a malware tracking and mitigation frame-work that makes use of honeypot technology in order to detect mali-cious traffic. Tartarus implements a dynamic quarantine technique to mitigate the spread of self propagating malware on a production net-work. In order to better understand the spread and impact of internet worms Tartarus is used to construct a detailed demographic of poten-tially malicious hosts on the internet. This host demographic is in turn used as a blacklist for firewall rule creation. The sources of malicious traffic is then illustrated through the use of a geolocation based visuali-sation.
- Full Text:
- Authors: Hunter, Samuel O , Irwin, Barry V W
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/428629 , vital:72525 , https://d1wqtxts1xzle7.cloudfront.net/96055420/Hunter-libre.pdf?1671479103=andresponse-content-disposi-tion=inline%3B+filename%3DTartarus_A_honeypot_based_malware_tracki.pdfandExpires=1714722666andSignature=JtPpR-IoAXILqsIJSlmCEvn6yyytE17YLQBeFJRKD5aBug-EbLxFpEGDf4GtQXHbxHvR4~E-b5QtMs1H6ruSYDti9fIHenRbLeepZTx9jYj92to3qZjy7UloigYbQuw0Y6sN95jI7d4HX-Xkspbz0~DsnzwFmLGopg7j9RZSHqpSpI~fBvlml3QQ2rLCm4aB9u8tSW8du5u~FiJgiLHNgJaPzEOzy4~yfKkXBh--LTFdgeAVYxQbOESGGh9k5bc-LDJhQ6dD5HpXsM3wKJvYuVyU6m83vT2scogVgKHIr-t~XuiqL35PfI3hs2c~ZO0TH4hCqwiNMHQ8GCYsLvllsA__andKey-Pair-Id=APKAJLOHF5GGSLRBV4ZA
- Description: On a daily basis many of the hosts connected to the Internet experi-ence continuous probing and attack from malicious entities. Detection and defence from these malicious entities has primarily been the con-cern of Intrusion Detection Systems, Intrusion Prevention Systems and Anti-Virus software. These systems rely heavily on known signatures to detect nefarious traffic. Due to the reliance on known malicious signa-tures, these systems have been at a serious disadvantage when it comes to detecting new, never before seen malware. This paper will introduce Tartarus which is a malware tracking and mitigation frame-work that makes use of honeypot technology in order to detect mali-cious traffic. Tartarus implements a dynamic quarantine technique to mitigate the spread of self propagating malware on a production net-work. In order to better understand the spread and impact of internet worms Tartarus is used to construct a detailed demographic of poten-tially malicious hosts on the internet. This host demographic is in turn used as a blacklist for firewall rule creation. The sources of malicious traffic is then illustrated through the use of a geolocation based visuali-sation.
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Teacher professional development with an Education for Sustainable Development focus in South Africa: Development of a network, curriculum framework and resources for teacher education
- Authors: Lotz-Sisitka, Heila
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/128949 , vital:36193 , https://www.ajol.info/index.php/sajee/article/view/122242
- Description: This national case study reports on the development of a national network, curriculum framework and resources for teacher education, with specific focus on the inclusion of environment and sustainability, also known as education for sustainable development (ESD) in the South African teacher education system. It reviews and reports on the history of environment and sustainability education in teacher education, and from this, the national case study begins to conceptualise a new approach to environment and sustainability teacher education within a new curriculum policy environment, and a new teacher education and development policy environment.Action research case study methodology is used to document the first phase of the emergence of this network, and this report covers Phase 1 of the initiative, which covers formation of the network, review of previous practices, three conceptual development pilot studies undertaken in both in-service and pre-service teacher education environments and a piloting of a ‘Train the Trainers’ or ‘Educate the Teacher Educators’ programme, which complements and extends the actual teacher education and development (TED) programme under development.The study highlights critical insights of relevance to the shift to a content referenced curriculum in South Africa, and shows how the ‘knowledge mix’ which forms the foundation of the new Teacher Education Qualifications Framework can be engaged. It also highlights some features of the changing knowledge environment, and what dominant knowledge practices are in environment and sustainability-related teaching and teacher education practices, opening these up for further scrutiny. It raises concerns that dominant knowledge work, while integrating a range of forms of knowledge (as is expected of the teacher education system under the new policy), tends to be limited by content on problems and issues for raising awareness, and fails to develop deeper conceptual depth and understanding of environment and sustainability, as issues based knowledge dominates. Similarly, it fails to support social innovation as a response to environment and sustainability concerns, as awareness raising dominates in dominant knowledge work. The study provides a revised conceptual framework for the Teacher Development Network (TEDN) programme, with guidance on key elements necessary to take the programme forward in Phase 2.
- Full Text:
- Authors: Lotz-Sisitka, Heila
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/128949 , vital:36193 , https://www.ajol.info/index.php/sajee/article/view/122242
- Description: This national case study reports on the development of a national network, curriculum framework and resources for teacher education, with specific focus on the inclusion of environment and sustainability, also known as education for sustainable development (ESD) in the South African teacher education system. It reviews and reports on the history of environment and sustainability education in teacher education, and from this, the national case study begins to conceptualise a new approach to environment and sustainability teacher education within a new curriculum policy environment, and a new teacher education and development policy environment.Action research case study methodology is used to document the first phase of the emergence of this network, and this report covers Phase 1 of the initiative, which covers formation of the network, review of previous practices, three conceptual development pilot studies undertaken in both in-service and pre-service teacher education environments and a piloting of a ‘Train the Trainers’ or ‘Educate the Teacher Educators’ programme, which complements and extends the actual teacher education and development (TED) programme under development.The study highlights critical insights of relevance to the shift to a content referenced curriculum in South Africa, and shows how the ‘knowledge mix’ which forms the foundation of the new Teacher Education Qualifications Framework can be engaged. It also highlights some features of the changing knowledge environment, and what dominant knowledge practices are in environment and sustainability-related teaching and teacher education practices, opening these up for further scrutiny. It raises concerns that dominant knowledge work, while integrating a range of forms of knowledge (as is expected of the teacher education system under the new policy), tends to be limited by content on problems and issues for raising awareness, and fails to develop deeper conceptual depth and understanding of environment and sustainability, as issues based knowledge dominates. Similarly, it fails to support social innovation as a response to environment and sustainability concerns, as awareness raising dominates in dominant knowledge work. The study provides a revised conceptual framework for the Teacher Development Network (TEDN) programme, with guidance on key elements necessary to take the programme forward in Phase 2.
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Teaching reading in Rukwangali in four Grade 3 Namibian classrooms : a case study
- Authors: Siyave, Theresia Nerumbu
- Date: 2011
- Subjects: Reading (Elementary) -- Namibia Reading teachers -- Training of -- Namibia Kwangali language -- Study and teaching (Elementary) -- Namibia Literacy -- Study and teaching (Elementary) -- Namibia Native language and education -- Study and teaching (Elementary) -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1798 , http://hdl.handle.net/10962/d1003683
- Description: This study aims to explore four grade 3 teachers’ understanding of teaching reading in Rukwangali, a home language in Namibia in Kavango region and to observe the strategies they use as well as the activities they set for their learners. During my School Based Studies (SBS), I noticed that learners were not reading with understanding. My interest was also stimulated by a study carried out in Namibia that found that the literacy levels for Namibian learners were poor compared to those of other African countries. This is a qualitative case study carried out within an interpretive paradigm. It seeks to understand the meaning that people attached to human actions. I selected the participants purposefully and in terms of convenience, as all three schools selected are situated in Rundu, the town in which I work as a college lecturer. The research tools I employed were semi-structured interviews, document analysis, classroom observation, and stimulated recall discussions on the lessons I observed. I used a variety of methods to triangulate data and enhance validity. This study reveals that teachers use multiple methods to teach reading. These methods include phonics and syllabification to help struggling learners to decode difficult and long (polysyllabic) words and the look-and-say method for whole word recognition and meaning making at word and sentence level. In addition, they also use the thematic approach to teaching and learning to expand learners’ vocabulary and enhance their understanding of the texts they read and to make their lessons learnercentred. However, the problems of language, lack of reading books written in Rukwangali and large class sizes constrain the teachers from teaching in a more learner-centred way. Therefore, the study gives some tentative recommendations to remedy this situation.
- Full Text:
- Authors: Siyave, Theresia Nerumbu
- Date: 2011
- Subjects: Reading (Elementary) -- Namibia Reading teachers -- Training of -- Namibia Kwangali language -- Study and teaching (Elementary) -- Namibia Literacy -- Study and teaching (Elementary) -- Namibia Native language and education -- Study and teaching (Elementary) -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1798 , http://hdl.handle.net/10962/d1003683
- Description: This study aims to explore four grade 3 teachers’ understanding of teaching reading in Rukwangali, a home language in Namibia in Kavango region and to observe the strategies they use as well as the activities they set for their learners. During my School Based Studies (SBS), I noticed that learners were not reading with understanding. My interest was also stimulated by a study carried out in Namibia that found that the literacy levels for Namibian learners were poor compared to those of other African countries. This is a qualitative case study carried out within an interpretive paradigm. It seeks to understand the meaning that people attached to human actions. I selected the participants purposefully and in terms of convenience, as all three schools selected are situated in Rundu, the town in which I work as a college lecturer. The research tools I employed were semi-structured interviews, document analysis, classroom observation, and stimulated recall discussions on the lessons I observed. I used a variety of methods to triangulate data and enhance validity. This study reveals that teachers use multiple methods to teach reading. These methods include phonics and syllabification to help struggling learners to decode difficult and long (polysyllabic) words and the look-and-say method for whole word recognition and meaning making at word and sentence level. In addition, they also use the thematic approach to teaching and learning to expand learners’ vocabulary and enhance their understanding of the texts they read and to make their lessons learnercentred. However, the problems of language, lack of reading books written in Rukwangali and large class sizes constrain the teachers from teaching in a more learner-centred way. Therefore, the study gives some tentative recommendations to remedy this situation.
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Teaching struggling adolescent readers in Namibia : a case study
- Authors: Simanga, Elizabeth Miyaze
- Date: 2011
- Subjects: Reading (Secondary) -- Namibia Reading comprehension -- Study and teaching (Secondary) -- Namibia Reading -- Remedial teaching -- Namibia Reading teachers -- Training of -- Namibia Second language acquisition -- Namibia English language -- Study and teaching -- Foreign speakers -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1876 , http://hdl.handle.net/10962/d1005639
- Description: Though research has been conducted on many issues since Namibia's independence in 1990, none of these studies has investigated how English Second Language (ESL) teachers teach and support struggling adolescent readers (SARs) to read. Utilising qualitative research techniques such as classroom observations, semi-structured interviews and document analysis, this case study looked at strategies, methods, and resources used by five ESL secondary school teachers to teach SARs to read in two regions in Namibia, Caprivi and Otjozondjupa regions. Two of the five participants were male teachers. The presence of SARs in the classes observed was established by using informal methods such as the ESL teachers' experience (Caprivi region), while a sample of questions from PIRLS 2001 (Mullis, Martin, Gonzalez, & Kennedy (2003) was compiled to form a test used in the Otjozondjupa region. The findings show that despite undergoing initial teacher training and majoring in English, the five ESL secondary school teachers were not trained to teach SARs either how to read or how to support them. In addition, the study found that there was a shortage of reading materials in all five selected schools.
- Full Text:
- Authors: Simanga, Elizabeth Miyaze
- Date: 2011
- Subjects: Reading (Secondary) -- Namibia Reading comprehension -- Study and teaching (Secondary) -- Namibia Reading -- Remedial teaching -- Namibia Reading teachers -- Training of -- Namibia Second language acquisition -- Namibia English language -- Study and teaching -- Foreign speakers -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1876 , http://hdl.handle.net/10962/d1005639
- Description: Though research has been conducted on many issues since Namibia's independence in 1990, none of these studies has investigated how English Second Language (ESL) teachers teach and support struggling adolescent readers (SARs) to read. Utilising qualitative research techniques such as classroom observations, semi-structured interviews and document analysis, this case study looked at strategies, methods, and resources used by five ESL secondary school teachers to teach SARs to read in two regions in Namibia, Caprivi and Otjozondjupa regions. Two of the five participants were male teachers. The presence of SARs in the classes observed was established by using informal methods such as the ESL teachers' experience (Caprivi region), while a sample of questions from PIRLS 2001 (Mullis, Martin, Gonzalez, & Kennedy (2003) was compiled to form a test used in the Otjozondjupa region. The findings show that despite undergoing initial teacher training and majoring in English, the five ESL secondary school teachers were not trained to teach SARs either how to read or how to support them. In addition, the study found that there was a shortage of reading materials in all five selected schools.
- Full Text: