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:
- Date Issued: 2011
- 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:
- Date Issued: 2011
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:
- Date Issued: 2011
- 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:
- Date Issued: 2011
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:
- Date Issued: 2011
- 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:
- Date Issued: 2011
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:
- Date Issued: 2011
- 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:
- Date Issued: 2011
Rhodes University Graduation Ceremony 2011
- Authors: Rhodes University
- Date: 2011
- Language: English
- Type: text
- Identifier: vital:8136 , http://hdl.handle.net/10962/d1007246
- Description: Rhodes University Graduation Ceremonies [at] 1820 Settlers National Monument Thursday, 7 April at 18.00 [and] Friday, 8 April at 10:30; 14:30 & 18:00 [and] Saturday, 9 April at 10:30
- Full Text:
- Date Issued: 2011
- Authors: Rhodes University
- Date: 2011
- Language: English
- Type: text
- Identifier: vital:8136 , http://hdl.handle.net/10962/d1007246
- Description: Rhodes University Graduation Ceremonies [at] 1820 Settlers National Monument Thursday, 7 April at 18.00 [and] Friday, 8 April at 10:30; 14:30 & 18:00 [and] Saturday, 9 April at 10:30
- Full Text:
- Date Issued: 2011
Characterization and electrocatalytic applications of metallophthalocyanine-single walled carbon nanotube conjugates
- Authors: Mugadza, Tawanda
- Date: 2011 , 2011-03-30
- Subjects: Phthalocyanines Pesticides Nanotubes Electrocatalysis Electrochemistry Transmission electron microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4419 , http://hdl.handle.net/10962/d1006855
- Description: Metallophthalocyanine-single walled carbon nanotube conjugates were successfully synthesized and applied in the electrochemical characterizations of pesticides (amitrole and diuron) and 2-mercaptoethanol (2-ME). The formation of conjugates was confirmed through the use of the following analytical techniques: UV-vis, FTIR, Raman and XRD spectroscopies, atomic force and transmission electron microscopies and voltammetry. Chemically linking SWCNT to MPcs created platforms that offered efficient transfer of electrons and this was confirmed through electrochemical impedance studies (EIS) and voltammetry as shown by lower ΔEp values observed in conjugates. Carboxy carrying MPcs have very poor electron transfer kinetics (both tetrasubstituted and low symmetry), but the presence of SWCNTs activates their catalysis. All electrochemical studies were done at pH 4. Cyclic voltammetry, rotating disk linear sweep voltammetry, chronoamperometry and EIS were used in the electrochemical characterization of 2-ME and the pesticides on poly-Ni(OH)TAPc and MPc-SWCNT modified glassy carbon electrodes (GCEs). High Tafel slopes were observed for the pesticides relative to 2-ME, an indication of the passivating nature of their oxidation products. However, conjugates showed very high resistances to passivation and were easily regenerated by shaking in methanol. Improved catalysis of the conjugates is also indicated by the high catalytic rate constants for the analytes, observed on these electrodes. Conjugates of low symmetry MPcs with SWCNTs gave the highest catalytic rate constants, confirming better catalysis on these electrode surfaces. The nature of SWCNT functionalization also affected catalysis, with amine functionalized SWCNTs inducing better catalytic properties into the MPcs than carboxylic acid terminated CNTs. The presence of amine functionalized SWCNTs activates the catalysis of non-catalytic carboxy-carrying MPcs and this is more pronounced in conjugates of tetrasubstituted MPcs relative to those of low symmetry Pcs. Ethylene amine (EA) functionalized SWCNTs reduced redox overpotentials of the MPcs more than the phenyl-amine (PA) functionalized counterparts. Poly-NiTAPc was successfully converted to poly-Ni(OH)TAPc through cyclisation in pH 4 buffer and showed very good catalytic properties towards diuron, relative to the former.
- Full Text:
- Date Issued: 2011
- Authors: Mugadza, Tawanda
- Date: 2011 , 2011-03-30
- Subjects: Phthalocyanines Pesticides Nanotubes Electrocatalysis Electrochemistry Transmission electron microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4419 , http://hdl.handle.net/10962/d1006855
- Description: Metallophthalocyanine-single walled carbon nanotube conjugates were successfully synthesized and applied in the electrochemical characterizations of pesticides (amitrole and diuron) and 2-mercaptoethanol (2-ME). The formation of conjugates was confirmed through the use of the following analytical techniques: UV-vis, FTIR, Raman and XRD spectroscopies, atomic force and transmission electron microscopies and voltammetry. Chemically linking SWCNT to MPcs created platforms that offered efficient transfer of electrons and this was confirmed through electrochemical impedance studies (EIS) and voltammetry as shown by lower ΔEp values observed in conjugates. Carboxy carrying MPcs have very poor electron transfer kinetics (both tetrasubstituted and low symmetry), but the presence of SWCNTs activates their catalysis. All electrochemical studies were done at pH 4. Cyclic voltammetry, rotating disk linear sweep voltammetry, chronoamperometry and EIS were used in the electrochemical characterization of 2-ME and the pesticides on poly-Ni(OH)TAPc and MPc-SWCNT modified glassy carbon electrodes (GCEs). High Tafel slopes were observed for the pesticides relative to 2-ME, an indication of the passivating nature of their oxidation products. However, conjugates showed very high resistances to passivation and were easily regenerated by shaking in methanol. Improved catalysis of the conjugates is also indicated by the high catalytic rate constants for the analytes, observed on these electrodes. Conjugates of low symmetry MPcs with SWCNTs gave the highest catalytic rate constants, confirming better catalysis on these electrode surfaces. The nature of SWCNT functionalization also affected catalysis, with amine functionalized SWCNTs inducing better catalytic properties into the MPcs than carboxylic acid terminated CNTs. The presence of amine functionalized SWCNTs activates the catalysis of non-catalytic carboxy-carrying MPcs and this is more pronounced in conjugates of tetrasubstituted MPcs relative to those of low symmetry Pcs. Ethylene amine (EA) functionalized SWCNTs reduced redox overpotentials of the MPcs more than the phenyl-amine (PA) functionalized counterparts. Poly-NiTAPc was successfully converted to poly-Ni(OH)TAPc through cyclisation in pH 4 buffer and showed very good catalytic properties towards diuron, relative to the former.
- Full Text:
- Date Issued: 2011
The problems of proving actual or apparent bias: an analysis of contemporary developments in South Africa
- Okpaluba, Chuks, Juma, Laurence
- Authors: Okpaluba, Chuks , Juma, Laurence
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/127498 , vital:36017 , https://doi.org/10.17159/1727-3781/2011/v14i7a2616
- Description: This article takes a critical look at the divergent approaches of courts in constructing the meaning of actual and apparent bias in adjudicative contexts. It argues that while proving actual bias on the part of an adjudicator may not always be easy and parties often revert to apprehended bias, an allegation of bias in any adjudication process is a matter that courts take very seriously. This notwithstanding, the courts have failed to consistently demarcate the necessary elements and threshold of proof that complainants must overcome to secure a successful challenge of decisions based on adjudicative impartiality. Upon critical evaluation of the decisions on the subject so far rendered, this article suggests that the pattern which has seemingly emerged is that which weighs the allegations of bias against the presumption of impartiality and the requirements of the double reasonableness test.
- Full Text:
- Date Issued: 2011
- Authors: Okpaluba, Chuks , Juma, Laurence
- Date: 2011
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/127498 , vital:36017 , https://doi.org/10.17159/1727-3781/2011/v14i7a2616
- Description: This article takes a critical look at the divergent approaches of courts in constructing the meaning of actual and apparent bias in adjudicative contexts. It argues that while proving actual bias on the part of an adjudicator may not always be easy and parties often revert to apprehended bias, an allegation of bias in any adjudication process is a matter that courts take very seriously. This notwithstanding, the courts have failed to consistently demarcate the necessary elements and threshold of proof that complainants must overcome to secure a successful challenge of decisions based on adjudicative impartiality. Upon critical evaluation of the decisions on the subject so far rendered, this article suggests that the pattern which has seemingly emerged is that which weighs the allegations of bias against the presumption of impartiality and the requirements of the double reasonableness test.
- Full Text:
- Date Issued: 2011
The role of Hsp90 in the Wnt pathway of MCF7 breast cancer cells
- Authors: Cooper, Leanne Claire
- Date: 2011
- Subjects: Cancer -- Treatment , Heat shock proteins , Cancer cells , Molecular chaperones
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3985 , http://hdl.handle.net/10962/d1004044 , Cancer -- Treatment , Heat shock proteins , Cancer cells , Molecular chaperones
- Description: Breast cancer is one of the most common forms of cancer in not only South African women, but women all over the world. The molecular chaperone heat shock protein 90 (HSP90) is upregulated in cancer and is almost exclusively associated with proteins involved in intracellular signal transduction, thus it plays an important role in signalling pathways within the cell. In cancer, there is an aberrant activation of the Wnt signaling pathway, which results in stabilized β-catenin being able to translocate to the nucleus where it can trigger the transcription of oncogenes found to be involved in the self-renewal of cells. The level of β-catenin is usually kept in check by a destruction complex comprising glycogen synthase kinase 3-beta (GSK-3β), axin1, adenomatous polyposis coli (APC) which phosphorylate β-catenin, resulting in its ubiquitination and degradation. HSP90 has been found to be associated with GSK-3β, but whether this association is only transient is debatable. Very little is known about the association of HSP90 with other members of the Wnt pathway in breast cancer. In this study, we have attempted to further identify the direct associations between HSP90 and GSK-3β, β-catenin, p-β-catenin and axin1. Immunofluorescence and confocal microscopy co-localization studies suggested a potential association between HSP90 and these proteins. Treatment with HSP90 inhibitors, 17-AAG and novobiocin resulted in a shift of axin1 to what appeared to be the plasma membrane. The associations of HSP90 with GSK-3β, β-catenin, p-β-catenin and axin1 were confirmed biochemically by co-immunoprecipitation and inhibition using 17-AAG, geldanamycin and novobiocin. We showed, for the first time that HSP90 is associated in a possible complex with β-catenin, p-β-catenin and axin1 therefore is potentially involved in the modulation of p-β-catenin in the Wnt pathway through the stabilization of the destruction complex.
- Full Text:
- Date Issued: 2011
- Authors: Cooper, Leanne Claire
- Date: 2011
- Subjects: Cancer -- Treatment , Heat shock proteins , Cancer cells , Molecular chaperones
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3985 , http://hdl.handle.net/10962/d1004044 , Cancer -- Treatment , Heat shock proteins , Cancer cells , Molecular chaperones
- Description: Breast cancer is one of the most common forms of cancer in not only South African women, but women all over the world. The molecular chaperone heat shock protein 90 (HSP90) is upregulated in cancer and is almost exclusively associated with proteins involved in intracellular signal transduction, thus it plays an important role in signalling pathways within the cell. In cancer, there is an aberrant activation of the Wnt signaling pathway, which results in stabilized β-catenin being able to translocate to the nucleus where it can trigger the transcription of oncogenes found to be involved in the self-renewal of cells. The level of β-catenin is usually kept in check by a destruction complex comprising glycogen synthase kinase 3-beta (GSK-3β), axin1, adenomatous polyposis coli (APC) which phosphorylate β-catenin, resulting in its ubiquitination and degradation. HSP90 has been found to be associated with GSK-3β, but whether this association is only transient is debatable. Very little is known about the association of HSP90 with other members of the Wnt pathway in breast cancer. In this study, we have attempted to further identify the direct associations between HSP90 and GSK-3β, β-catenin, p-β-catenin and axin1. Immunofluorescence and confocal microscopy co-localization studies suggested a potential association between HSP90 and these proteins. Treatment with HSP90 inhibitors, 17-AAG and novobiocin resulted in a shift of axin1 to what appeared to be the plasma membrane. The associations of HSP90 with GSK-3β, β-catenin, p-β-catenin and axin1 were confirmed biochemically by co-immunoprecipitation and inhibition using 17-AAG, geldanamycin and novobiocin. We showed, for the first time that HSP90 is associated in a possible complex with β-catenin, p-β-catenin and axin1 therefore is potentially involved in the modulation of p-β-catenin in the Wnt pathway through the stabilization of the destruction complex.
- Full Text:
- Date Issued: 2011
A study of a class of invariant optimal control problems on the Euclidean group SE(2)
- Authors: Adams, Ross Montague
- Date: 2011
- Subjects: Matrix groups Lie groups Extremal problems (Mathematics) Maximum principles (Mathematics) Hamilton-Jacobi equations Lyapunov stability
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5420 , http://hdl.handle.net/10962/d1006060
- Description: The aim of this thesis is to study a class of left-invariant optimal control problems on the matrix Lie group SE(2). We classify, under detached feedback equivalence, all controllable (left-invariant) control affine systems on SE(2). This result produces six types of control affine systems on SE(2). Hence, we study six associated left-invariant optimal control problems on SE(2). A left-invariant optimal control problem consists of minimizing a cost functional over the trajectory-control pairs of a left-invariant control system subject to appropriate boundary conditions. Each control problem is lifted from SE(2) to T*SE(2) ≅ SE(2) x se (2)*and then reduced to a problem on se (2)*. The maximum principle is used to obtain the optimal control and Hamiltonian corresponding to the normal extremals. Then we derive the (reduced) extremal equations on se (2)*. These equations are explicitly integrated by trigonometric and Jacobi elliptic functions. Finally, we fully classify, under Lyapunov stability, the equilibrium states of the normal extremal equations for each of the six types under consideration.
- Full Text:
- Date Issued: 2011
- Authors: Adams, Ross Montague
- Date: 2011
- Subjects: Matrix groups Lie groups Extremal problems (Mathematics) Maximum principles (Mathematics) Hamilton-Jacobi equations Lyapunov stability
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5420 , http://hdl.handle.net/10962/d1006060
- Description: The aim of this thesis is to study a class of left-invariant optimal control problems on the matrix Lie group SE(2). We classify, under detached feedback equivalence, all controllable (left-invariant) control affine systems on SE(2). This result produces six types of control affine systems on SE(2). Hence, we study six associated left-invariant optimal control problems on SE(2). A left-invariant optimal control problem consists of minimizing a cost functional over the trajectory-control pairs of a left-invariant control system subject to appropriate boundary conditions. Each control problem is lifted from SE(2) to T*SE(2) ≅ SE(2) x se (2)*and then reduced to a problem on se (2)*. The maximum principle is used to obtain the optimal control and Hamiltonian corresponding to the normal extremals. Then we derive the (reduced) extremal equations on se (2)*. These equations are explicitly integrated by trigonometric and Jacobi elliptic functions. Finally, we fully classify, under Lyapunov stability, the equilibrium states of the normal extremal equations for each of the six types under consideration.
- Full Text:
- Date Issued: 2011
Trophodynamics of the benthic and hyperbenthic communities inhabiting the Sub-Antarctic Prince Edward Islands : stable isotope and fatty acid signatures
- Authors: Allan, Elizabeth Louise
- Date: 2011
- Subjects: Benthos -- Prince Edward Islands Benthos -- Feeding and feeds -- Prince Edward Islands Benthos -- Nutrition -- Prince Edward Islands Prince Edward Islands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5806 , http://hdl.handle.net/10962/d1006350
- Description: The aim of this study was to investigate spatial changes in the trophic and energy pathways of the benthic community in the shallow shelf waters of the sub-Antarctic Prince Edward Islands (PEI). A combination of stable isotope and fatty acid analyses were used to provide a time-integrated view of the assimilated feeding history of selected components of the PEI benthic community. This study forms part of the larger project entitled “Variability in the Southern Ocean ecosystems” and is a contribution to the South African National Antarctic Programme (SANAP). During austral autumn 2009, benthic specimens were collected from 10 stations (from depths of 70 to 295 m) in different regions around the PEI: inter-island shelf (upstream, between and downstream of the islands) and nearshore. Historical data were combined with new data collected during 2009 to assess the long-term trends in the feeding ecology of the benthos in the region of the islands. The stable isotope and fatty acid signatures of the benthic suspension- and deposit-feeding organisms generated during this study suggested that these two communities incorporated both phytoplankton and kelp in their diets. Stable isotope, and to a lesser extent fatty acid signatures, indicated that kelp contributed more to the diets of those organisms in close proximity to the kelp beds (nearshore stations) than those from the inter-island region. Overall, however, pelagic phytoplankton was the dominant food source in the diets of all organisms, even for those living near the kelp beds. Notable exceptions were the sponges and bryozoans, in which kelp and phytoplankton contributed similar proportions to their diets, most likely resulting from a size restricted feeding mode. There were, therefore, no distinct spatial differences in the importance of the various food sources. However, fatty acid compositional data indicated increased food quality between and within the lee of the islands compared to upstream. The organisms collected upstream of the PEI had substantially lower quantities of total fatty acids (TFAs) than organisms of the same species collected from nearshore, open shelf or downstream stations. The increased food quality between and within the lee of the islands was likely a result of the “island mass effect”, which reflects increased phytoplankton concentrations at the PEI. The fatty acid profiles of hyperbenthic shrimp Nauticaris marionis, a key species in the PEI ecosystem, revealed no distinct ontogenetic or spatial patterns. This result is in contrast to the stable isotope analyses, which detected both spatial and ontogenetic differences in the diet of the shrimp. Nearshore shrimp were more ₁₃C-enriched than those from the inter-island region, suggesting increased kelp entering the food web within these regions. In addition, the shrimps demonstrated enrichment in δ₁₃C and δ₁₅N signatures with an increase in size, resulting in a relatively distinct separation of size classes, thus reflecting niche separation through their diets. The fatty acid profiles revealed that the shrimp all contained large proportions of polyunsaturated fatty acids (PUFAs) and essential fatty acids (EFAs), indicating that the quality of food consumed was similar among size class and region despite the niche separation and variation in carbon sources utilised. In addition, diatom and dinoflagellate fatty acids (20:5ω3 and 22:6ω3, respectively) occurred in the highest proportions in N. marionis, highlighting the importance of phytoplankton (indirectly) in their diet. These results represent strong evidence that phytoplankton is an importance food source in the PEI ecosystem. The temporal investigation of isotope signatures in the benthos at the PEI indicated that N. marionis demonstrated an overall depletion in δ₁₃C signatures over the period of 1984 to 2009 (nearshore: -2.55 ‰, inter-island: -2.32 ‰). Overall, the benthic community showed similar depletions in δ13C signatures (from -1.96 to -4.70 ‰), suggesting that shifts have occurred in the carbon signatures at the base of the food web. The depletion in δ₁₃C signatures of the benthos at the PEI most likely reflects increased contributions of smaller slow growing phytoplankton cells (more depleted signatures than large fast growing cells) in the diets of these organisms over time. These diet shifts, in turn, suggest a decrease in productivity has occurred at the islands, likely due to a decreased frequency and intensity of the “island mass effect”. Decreased phytoplankton productivity at the PEI likely results from the southward shift in the average position of the sub-Antarctic Front (SAF), most likely in response to climate change, which in turn promotes flow-through conditions rather than retention at the PEI.
- Full Text:
- Date Issued: 2011
- Authors: Allan, Elizabeth Louise
- Date: 2011
- Subjects: Benthos -- Prince Edward Islands Benthos -- Feeding and feeds -- Prince Edward Islands Benthos -- Nutrition -- Prince Edward Islands Prince Edward Islands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5806 , http://hdl.handle.net/10962/d1006350
- Description: The aim of this study was to investigate spatial changes in the trophic and energy pathways of the benthic community in the shallow shelf waters of the sub-Antarctic Prince Edward Islands (PEI). A combination of stable isotope and fatty acid analyses were used to provide a time-integrated view of the assimilated feeding history of selected components of the PEI benthic community. This study forms part of the larger project entitled “Variability in the Southern Ocean ecosystems” and is a contribution to the South African National Antarctic Programme (SANAP). During austral autumn 2009, benthic specimens were collected from 10 stations (from depths of 70 to 295 m) in different regions around the PEI: inter-island shelf (upstream, between and downstream of the islands) and nearshore. Historical data were combined with new data collected during 2009 to assess the long-term trends in the feeding ecology of the benthos in the region of the islands. The stable isotope and fatty acid signatures of the benthic suspension- and deposit-feeding organisms generated during this study suggested that these two communities incorporated both phytoplankton and kelp in their diets. Stable isotope, and to a lesser extent fatty acid signatures, indicated that kelp contributed more to the diets of those organisms in close proximity to the kelp beds (nearshore stations) than those from the inter-island region. Overall, however, pelagic phytoplankton was the dominant food source in the diets of all organisms, even for those living near the kelp beds. Notable exceptions were the sponges and bryozoans, in which kelp and phytoplankton contributed similar proportions to their diets, most likely resulting from a size restricted feeding mode. There were, therefore, no distinct spatial differences in the importance of the various food sources. However, fatty acid compositional data indicated increased food quality between and within the lee of the islands compared to upstream. The organisms collected upstream of the PEI had substantially lower quantities of total fatty acids (TFAs) than organisms of the same species collected from nearshore, open shelf or downstream stations. The increased food quality between and within the lee of the islands was likely a result of the “island mass effect”, which reflects increased phytoplankton concentrations at the PEI. The fatty acid profiles of hyperbenthic shrimp Nauticaris marionis, a key species in the PEI ecosystem, revealed no distinct ontogenetic or spatial patterns. This result is in contrast to the stable isotope analyses, which detected both spatial and ontogenetic differences in the diet of the shrimp. Nearshore shrimp were more ₁₃C-enriched than those from the inter-island region, suggesting increased kelp entering the food web within these regions. In addition, the shrimps demonstrated enrichment in δ₁₃C and δ₁₅N signatures with an increase in size, resulting in a relatively distinct separation of size classes, thus reflecting niche separation through their diets. The fatty acid profiles revealed that the shrimp all contained large proportions of polyunsaturated fatty acids (PUFAs) and essential fatty acids (EFAs), indicating that the quality of food consumed was similar among size class and region despite the niche separation and variation in carbon sources utilised. In addition, diatom and dinoflagellate fatty acids (20:5ω3 and 22:6ω3, respectively) occurred in the highest proportions in N. marionis, highlighting the importance of phytoplankton (indirectly) in their diet. These results represent strong evidence that phytoplankton is an importance food source in the PEI ecosystem. The temporal investigation of isotope signatures in the benthos at the PEI indicated that N. marionis demonstrated an overall depletion in δ₁₃C signatures over the period of 1984 to 2009 (nearshore: -2.55 ‰, inter-island: -2.32 ‰). Overall, the benthic community showed similar depletions in δ13C signatures (from -1.96 to -4.70 ‰), suggesting that shifts have occurred in the carbon signatures at the base of the food web. The depletion in δ₁₃C signatures of the benthos at the PEI most likely reflects increased contributions of smaller slow growing phytoplankton cells (more depleted signatures than large fast growing cells) in the diets of these organisms over time. These diet shifts, in turn, suggest a decrease in productivity has occurred at the islands, likely due to a decreased frequency and intensity of the “island mass effect”. Decreased phytoplankton productivity at the PEI likely results from the southward shift in the average position of the sub-Antarctic Front (SAF), most likely in response to climate change, which in turn promotes flow-through conditions rather than retention at the PEI.
- Full Text:
- Date Issued: 2011
The influence of endorsed professional surfers on consumer attitude towards surf brands
- Authors: Greybe, Frikkie
- Date: 2011
- Subjects: Brand name products , Branding (Marketing) , Surfers
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:8671 , http://hdl.handle.net/10948/d1008470 , Brand name products , Branding (Marketing) , Surfers
- Description: Sport, with the help of the media, plays a huge role in today’s society. Sport fans are following their favourite athlete and teams religiously as they compete locally and internationally. Over a century ago, the first professional athlete was endorsed. Since then companies are investing millions of dollars in athlete endorsement to promote brand awareness under consumers. The surfing industry is no different. With the Association of Professional Surfers (ASP) world tour, the big surf companies are jumping at the opportunity to sponsor pro surfers to market their products. Previous studies have shown athletes can evoke both positive and negative attitudes towards their endorsing brand thus effecting company’s sales. The aim of this study was to research the influence these endorsed pro surfers have on consumer behaviour towards their brand in a local market. A qualitative study was done on local surfers in Port Elizabeth, South Africa. Results showed that favourite surfers evoke a positive attitude towards their sponsoring brand. However this influence does not seem to be as significant as in other sports. Surf companies within the industry should be aware of the big influence age has on the consumers behaviour and that different age groups follow different surfers. Companies should choose to sponsor professional surfers that fit the image of the company and the products, not necessarily the professional surfer who performs the best. Using professional surfers in advertising of products does create better brand awareness, but endorsed professional surfers are not likely to change consumer’s perceptions of the endorsing brand’s products.
- Full Text:
- Date Issued: 2011
- Authors: Greybe, Frikkie
- Date: 2011
- Subjects: Brand name products , Branding (Marketing) , Surfers
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: vital:8671 , http://hdl.handle.net/10948/d1008470 , Brand name products , Branding (Marketing) , Surfers
- Description: Sport, with the help of the media, plays a huge role in today’s society. Sport fans are following their favourite athlete and teams religiously as they compete locally and internationally. Over a century ago, the first professional athlete was endorsed. Since then companies are investing millions of dollars in athlete endorsement to promote brand awareness under consumers. The surfing industry is no different. With the Association of Professional Surfers (ASP) world tour, the big surf companies are jumping at the opportunity to sponsor pro surfers to market their products. Previous studies have shown athletes can evoke both positive and negative attitudes towards their endorsing brand thus effecting company’s sales. The aim of this study was to research the influence these endorsed pro surfers have on consumer behaviour towards their brand in a local market. A qualitative study was done on local surfers in Port Elizabeth, South Africa. Results showed that favourite surfers evoke a positive attitude towards their sponsoring brand. However this influence does not seem to be as significant as in other sports. Surf companies within the industry should be aware of the big influence age has on the consumers behaviour and that different age groups follow different surfers. Companies should choose to sponsor professional surfers that fit the image of the company and the products, not necessarily the professional surfer who performs the best. Using professional surfers in advertising of products does create better brand awareness, but endorsed professional surfers are not likely to change consumer’s perceptions of the endorsing brand’s products.
- Full Text:
- Date Issued: 2011
Scoring an own goal? The Construction Workers 2010 World Cup Strike
- Authors: Cottle, Eddie
- Date: 2011-10-04
- Subjects: Labour disputes -- South Africa , Strikes and lockouts -- South Africa , Industrial relations -- South Africa
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/60018 , vital:27722
- Description: The nationwide strike by 70 000 construction workers between 8 and 15 July 2009 was unprecedented and significant in several respects. This was the first national strike on 2010 World Cup sites by South African construction workers and was therefore an historic event. A second key feature of the strike was the unity displayed by workers and trade unions within a sector organised by several trade unions. Engineering and building workers came out on strike, with the Building Construction & Allied Workers Union (BCAWU) and the National Union of Mineworkers (NUM) standing together as their representative organisations. A third feature of the strike was the widespread sympathy for it by the South African public and media. This was despite it potentially setting back progress with World Cup projects. Fourthly, the pressure placed upon the trade unions' negotiating team by the Ministry of Labour and the FIFA Local Organising Committee (LOC) proved lethal in undermining their, assisting in causing them to dilute their trade union demands and demobilising the national strike.
- Full Text:
- Date Issued: 2011-10-04
- Authors: Cottle, Eddie
- Date: 2011-10-04
- Subjects: Labour disputes -- South Africa , Strikes and lockouts -- South Africa , Industrial relations -- South Africa
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/60018 , vital:27722
- Description: The nationwide strike by 70 000 construction workers between 8 and 15 July 2009 was unprecedented and significant in several respects. This was the first national strike on 2010 World Cup sites by South African construction workers and was therefore an historic event. A second key feature of the strike was the unity displayed by workers and trade unions within a sector organised by several trade unions. Engineering and building workers came out on strike, with the Building Construction & Allied Workers Union (BCAWU) and the National Union of Mineworkers (NUM) standing together as their representative organisations. A third feature of the strike was the widespread sympathy for it by the South African public and media. This was despite it potentially setting back progress with World Cup projects. Fourthly, the pressure placed upon the trade unions' negotiating team by the Ministry of Labour and the FIFA Local Organising Committee (LOC) proved lethal in undermining their, assisting in causing them to dilute their trade union demands and demobilising the national strike.
- Full Text:
- Date Issued: 2011-10-04
a pH-metric speciation and anti-diabetic study of oxovanadium (IV) amino acid derivatives
- Authors: Gundhla, Isaac Zvikomborero
- Date: 2011 , 2011-03-15
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4399 , http://hdl.handle.net/10962/d1006691
- Description: Novel oxovanadium(IV) complexes of glycine, ʟ-alanine, 1-methylimidazole-2-carboxylic acid, imidazole-2-caboxylic acid and imidazole-4-carboxylic acid were synthesized and isolated in the solid state. The ligands and complexes were characterized by elemental analysis, melting point, NMR, IR and UV-vis spectroscopy. The IR studies showed that glycine and ʟ-alanine coordinate monodentately through the amine nitrogen whilst the imidazole-carboxylic acid derivatives assume a bidentate chelation. The electronic spectroscopic studies indicate distorted octahedral geometry for the oxovanadium complexes of amino acids and a square pyramidal geometry for oxovanadium(IV) complexes of imidazole carboxylic acid derivatives. The reaction of vanadyl (VO2+) with glycine, ʟ-alanine, imidazole-2-cabrboxylic acid, imidazole-4-carboxylic acid and 1-methylimidazole-2-carboxylic acid was studied in aqueous solution by pH-potentiometry under oxygen and carbon dioxide-free conditions. The data obtained from these titrations were used to calculate the protonation and stability constants. The results showed that all ligands are suitable for bidentate coordination in the formation of monomeric species although the solid state studies of the oxovanadium(IV) complexes of amino acids showed a monodentate coordination. The overall stability constants for the (VIVO)-ʟ-alanine system (log β120 = 18.27(6)), (VIVO)-glycine system (β120 = 17.22(6)), (VIVO)-imidazole-4-carboxyic acid (β120 = 11.38(8)), (VIVO)-imidazole-2-carboxylic acid (β120 = 11.62(6)) and (VIVO)-1-methylimidazole-2-carboxylic acid (β120 = 15.49(9)) were obtained. The calculations for the species distribution in the experimental pH range showed that the neutral bis-coordinated complexes are dominant over the biological pH range. The glucose uptake effect of oxovanadium(IV) complex of ʟ-alanine, imidazole-4-carboxylic acid, imidazole-2-carboxylic acid and 1-methylimidazole-2-carboxylic acid was investigated using 3T3-L1 adipocytes, Chang liver and C2C12 muscle cells at various concentrations. The compounds had significant glucose uptake on Chang liver cells only at a concentration of 0.1-10 μM whilst in the C2C12 muscle and 3T3-L1 cells the compounds showed little to no activity probably due to the lower concentrations employed as a result of the cytotoxicity of these compounds on these two cell lines.
- Full Text:
- Date Issued: 2011
- Authors: Gundhla, Isaac Zvikomborero
- Date: 2011 , 2011-03-15
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4399 , http://hdl.handle.net/10962/d1006691
- Description: Novel oxovanadium(IV) complexes of glycine, ʟ-alanine, 1-methylimidazole-2-carboxylic acid, imidazole-2-caboxylic acid and imidazole-4-carboxylic acid were synthesized and isolated in the solid state. The ligands and complexes were characterized by elemental analysis, melting point, NMR, IR and UV-vis spectroscopy. The IR studies showed that glycine and ʟ-alanine coordinate monodentately through the amine nitrogen whilst the imidazole-carboxylic acid derivatives assume a bidentate chelation. The electronic spectroscopic studies indicate distorted octahedral geometry for the oxovanadium complexes of amino acids and a square pyramidal geometry for oxovanadium(IV) complexes of imidazole carboxylic acid derivatives. The reaction of vanadyl (VO2+) with glycine, ʟ-alanine, imidazole-2-cabrboxylic acid, imidazole-4-carboxylic acid and 1-methylimidazole-2-carboxylic acid was studied in aqueous solution by pH-potentiometry under oxygen and carbon dioxide-free conditions. The data obtained from these titrations were used to calculate the protonation and stability constants. The results showed that all ligands are suitable for bidentate coordination in the formation of monomeric species although the solid state studies of the oxovanadium(IV) complexes of amino acids showed a monodentate coordination. The overall stability constants for the (VIVO)-ʟ-alanine system (log β120 = 18.27(6)), (VIVO)-glycine system (β120 = 17.22(6)), (VIVO)-imidazole-4-carboxyic acid (β120 = 11.38(8)), (VIVO)-imidazole-2-carboxylic acid (β120 = 11.62(6)) and (VIVO)-1-methylimidazole-2-carboxylic acid (β120 = 15.49(9)) were obtained. The calculations for the species distribution in the experimental pH range showed that the neutral bis-coordinated complexes are dominant over the biological pH range. The glucose uptake effect of oxovanadium(IV) complex of ʟ-alanine, imidazole-4-carboxylic acid, imidazole-2-carboxylic acid and 1-methylimidazole-2-carboxylic acid was investigated using 3T3-L1 adipocytes, Chang liver and C2C12 muscle cells at various concentrations. The compounds had significant glucose uptake on Chang liver cells only at a concentration of 0.1-10 μM whilst in the C2C12 muscle and 3T3-L1 cells the compounds showed little to no activity probably due to the lower concentrations employed as a result of the cytotoxicity of these compounds on these two cell lines.
- Full Text:
- Date Issued: 2011
Effects of selected modes of digital distribution on music consumerism, with reference to the album format
- Authors: Du Preez, Liska
- Date: 2011
- Subjects: Sound -- Recording and reproducing -- Digital techniques , Music -- Technological innovations , Music and the Internet
- Language: English
- Type: Thesis , Masters , MMus
- Identifier: vital:8504 , http://hdl.handle.net/10948/1427 , Sound -- Recording and reproducing -- Digital techniques , Music -- Technological innovations , Music and the Internet
- Description: In this digital age many listeners of music now purchase albums from online digital music stores instead of buying a physical album from the record store. This has created a concern with many regarding the future of the album as a physical medium. This study investigates the impact of the possible death of the album on certain listening habits, the activity of record collecting, the creation of large-scale musical works, music consumerism, and its implications for the creative process on music as art and sound-recording quality. Three realisations have led to the problem statement. Firstly, the album might not have a future in the digital age. Secondly, downloadable songs might not be able to recreate an album experience. The third realisation is that the possible death of the album could create new, exciting challenges to artists as they strive to create art. This study is exploratory in nature - and no hypothesis was generated. The research necessitates qualitative, exploratory, descriptive and contextual approaches. Furthermore, the investigation has led to the collection of mostly new data, constituting a “primary data design” through the implementation of qualitative listening experiments and a focus group, using full-time NMMU students between 18 and 25 years of age. It is herein argued that digital distribution might possibly have an effect on the perception of the album format and might possibly still be a relevant listening experience, valued by young people. Singles and albums are collectable; and good albums are considered artistic and comparable to the large-scale musical works of the past. If the concept of an album does not die out, then high fidelity formats should be able to re-invent the album experience. Listening experiences other than the album experience do exist, and they could generate new ways for artists to create musical art.
- Full Text:
- Date Issued: 2011
- Authors: Du Preez, Liska
- Date: 2011
- Subjects: Sound -- Recording and reproducing -- Digital techniques , Music -- Technological innovations , Music and the Internet
- Language: English
- Type: Thesis , Masters , MMus
- Identifier: vital:8504 , http://hdl.handle.net/10948/1427 , Sound -- Recording and reproducing -- Digital techniques , Music -- Technological innovations , Music and the Internet
- Description: In this digital age many listeners of music now purchase albums from online digital music stores instead of buying a physical album from the record store. This has created a concern with many regarding the future of the album as a physical medium. This study investigates the impact of the possible death of the album on certain listening habits, the activity of record collecting, the creation of large-scale musical works, music consumerism, and its implications for the creative process on music as art and sound-recording quality. Three realisations have led to the problem statement. Firstly, the album might not have a future in the digital age. Secondly, downloadable songs might not be able to recreate an album experience. The third realisation is that the possible death of the album could create new, exciting challenges to artists as they strive to create art. This study is exploratory in nature - and no hypothesis was generated. The research necessitates qualitative, exploratory, descriptive and contextual approaches. Furthermore, the investigation has led to the collection of mostly new data, constituting a “primary data design” through the implementation of qualitative listening experiments and a focus group, using full-time NMMU students between 18 and 25 years of age. It is herein argued that digital distribution might possibly have an effect on the perception of the album format and might possibly still be a relevant listening experience, valued by young people. Singles and albums are collectable; and good albums are considered artistic and comparable to the large-scale musical works of the past. If the concept of an album does not die out, then high fidelity formats should be able to re-invent the album experience. Listening experiences other than the album experience do exist, and they could generate new ways for artists to create musical art.
- Full Text:
- Date Issued: 2011
Curating the reviled, beloved and quotidian: a retrospective of Vladimir Tretchikoff
- Authors: Lamprecht, Andrew Paul
- Date: 2011
- Subjects: Tretchikoff, Vladimir -- Criticism and interpretation Painters -- South Africa -- Criticism and interpretation Curatorship -- South Africa -- Art Kitsch
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2407 , http://hdl.handle.net/10962/d1002203
- Description: This thesis aims to contextualise my curation of 'Tretchikoff: The People's Painter' at the Iziko South African National Gallery by outlining the process by which I came to embark on this project and to examine the concepts of mass art and kitsch in relation to the painter. Mass art, in Noel Carroll's explication of the term, is art that utilises industrial processes of replication. Carroll argues that this leads to specific formal and structural tendencies in this art which have much in common with the pejorative concept of kitsch, or art that is lacking in taste or effuses excessive emotion. The latter term was and continues to be applied to Tretchikoff. Although some have attempted to 'reclaim' the word as a positive concept the negative associations that link this term to Tretchikoff are strong. Interrogating these concepts led me to decide to curate TretchikofPs retrospective by focusing on his painting and not including the prints for which he was so well known. Awareness of the complex associations and 'received knowledge' that his prints engender has influenced several curatorial decisions that I have taken. I consider the intellectual underpinnings of my curatorial strategy and argue for an 'open' exhibition which gives the viewer the opportunity to assess his work and legacy in an objective manner, free from as much curatorial mediation and didacticsm as possible. There are no answers to be offered in my curation of Tretchikxiff the People's Painter, rather I have aimed to set up dialogues, discussions, confrontations and challenges; I have offered simple relationships rather than complex juxtapositions I have aimed to position the artwork as the centre of the engagement relative to the viewer.
- Full Text:
- Date Issued: 2011
- Authors: Lamprecht, Andrew Paul
- Date: 2011
- Subjects: Tretchikoff, Vladimir -- Criticism and interpretation Painters -- South Africa -- Criticism and interpretation Curatorship -- South Africa -- Art Kitsch
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2407 , http://hdl.handle.net/10962/d1002203
- Description: This thesis aims to contextualise my curation of 'Tretchikoff: The People's Painter' at the Iziko South African National Gallery by outlining the process by which I came to embark on this project and to examine the concepts of mass art and kitsch in relation to the painter. Mass art, in Noel Carroll's explication of the term, is art that utilises industrial processes of replication. Carroll argues that this leads to specific formal and structural tendencies in this art which have much in common with the pejorative concept of kitsch, or art that is lacking in taste or effuses excessive emotion. The latter term was and continues to be applied to Tretchikoff. Although some have attempted to 'reclaim' the word as a positive concept the negative associations that link this term to Tretchikoff are strong. Interrogating these concepts led me to decide to curate TretchikofPs retrospective by focusing on his painting and not including the prints for which he was so well known. Awareness of the complex associations and 'received knowledge' that his prints engender has influenced several curatorial decisions that I have taken. I consider the intellectual underpinnings of my curatorial strategy and argue for an 'open' exhibition which gives the viewer the opportunity to assess his work and legacy in an objective manner, free from as much curatorial mediation and didacticsm as possible. There are no answers to be offered in my curation of Tretchikxiff the People's Painter, rather I have aimed to set up dialogues, discussions, confrontations and challenges; I have offered simple relationships rather than complex juxtapositions I have aimed to position the artwork as the centre of the engagement relative to the viewer.
- Full Text:
- Date Issued: 2011
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:
- Date Issued: 2011
- 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:
- Date Issued: 2011
Nanomaterial modified electrodes : optimization of voltammetric sensors for pharmaceutical and industrial application
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
- Date Issued: 2011
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
- Date Issued: 2011
Evaluating long term effects of fire frequency on soil seed bank composition and species diversity in a semi-arid , South African savanna
- Mabuza, Thembisile Veronicah
- Authors: Mabuza, Thembisile Veronicah
- Date: 2011
- Subjects: Pastures -- South Africa -- Eastern Cape , Fire management -- South Africa -- Eastern Cape , Forage plants -- Evaluation , Ruminants -- Feeding and feeds , Ruminants -- Nutrition , Soil seed banks
- Language: English
- Type: Thesis , Masters , MSc Agric (Pasture Science)
- Identifier: vital:11579 , http://hdl.handle.net/10353/346 , Pastures -- South Africa -- Eastern Cape , Fire management -- South Africa -- Eastern Cape , Forage plants -- Evaluation , Ruminants -- Feeding and feeds , Ruminants -- Nutrition , Soil seed banks
- Description: Fire is generally used as a management tool for different vegetation types such as savannas and grasslands in southern Africa. In the False Thornveld of the Eastern Cape, fire is commonly used to control bush encroachment and to increase grass production, as grasses are important source of forage for domestic livestock. At the University of Fort Hare farm in the Eastern Cape, a trial was set up in 1980 to investigate the effect of burning frequency on vegetation. There are six treatments replicated twice in a completely randomized design on a 100 m x 50 m plots. The treatments comprise no burn, annual, biennial, triennial, quadrennial and sexennial burns. From this trial a study was conducted to investigate long term effect of burning frequency on species and soil seed bank diversity. Two 100 m line transects located 25 m apart were laid within each plot, and the herbaceous and woody species were identified and recorded along the line transects. Relative abundances (%) for each species were calculated for each treatment. Soil samples were collected at an interval of 13.3 m along the line transects. The samples were placed in paper bags and kept for use in a germination experiment. The seedling emergence germination method was used in the glasshouse to determine emerging seedlings, pots were filled with Hygromix growth medium and the soils from the fire trials 12 X 6 = 72 were spread on top. Soil from the control plots were also pre-treated with heat, smoke and the combination of heat and smoke. The experiment started in January 2010 and was terminated in April 2010. The Shannon-Weaver Diversity Index was used to determine species diversity for standing vegetation and germinated seedlings. Data were tested for normality and species abundances were transformed. Analysis of Variance (ANOVA) was applied to test treatment effects on geminated seedlings, species abundance and diversity at α = 0.05 significance level. Significant differences between treatment means were determined by post v hoc tests using Fischer‟s Least Significant Difference test at α = 0.05. The Pearson Moment Correlation test was used to test the relationship between vegetation and soil seed banks. Treatments had significant effects on herbaceous, woody species abundance and diversity (P < 0.05), but there was no significant treatment effect on soil seed bank diversity and on pre-germination treatments (P > 0.05). The annual, biennial and triennial burns were dominated by Themeda triandra while the quadrennial, sexennial and the control treatments were dominated by Sporobolus fimbriatus and Melica decumbens. A. karroo dominated the woody component across all treatments, but it did not change in abundance. S. fimbriatus was the most abundant in the soil seed bank across all the treatments and also in all pre-germination treatments. Species diversity was high in standing vegetation in the quadrennial, sexennial and the control treatments. There was no significant correlation between the standing vegetation and soil seed bank diversities (P > 0.05). Based on these findings it is apparent that fire can change vegetation in an area to be dominated by fire tolerant or fire intolerant species. Fire frequency, heat and smoke affects soil seed banks to a lesser extent in the False Thornveld. For the management of the False Thornveld of the Eastern Cape, less frequent burning is recommended as it increases aboveground species diversity.
- Full Text:
- Date Issued: 2011
- Authors: Mabuza, Thembisile Veronicah
- Date: 2011
- Subjects: Pastures -- South Africa -- Eastern Cape , Fire management -- South Africa -- Eastern Cape , Forage plants -- Evaluation , Ruminants -- Feeding and feeds , Ruminants -- Nutrition , Soil seed banks
- Language: English
- Type: Thesis , Masters , MSc Agric (Pasture Science)
- Identifier: vital:11579 , http://hdl.handle.net/10353/346 , Pastures -- South Africa -- Eastern Cape , Fire management -- South Africa -- Eastern Cape , Forage plants -- Evaluation , Ruminants -- Feeding and feeds , Ruminants -- Nutrition , Soil seed banks
- Description: Fire is generally used as a management tool for different vegetation types such as savannas and grasslands in southern Africa. In the False Thornveld of the Eastern Cape, fire is commonly used to control bush encroachment and to increase grass production, as grasses are important source of forage for domestic livestock. At the University of Fort Hare farm in the Eastern Cape, a trial was set up in 1980 to investigate the effect of burning frequency on vegetation. There are six treatments replicated twice in a completely randomized design on a 100 m x 50 m plots. The treatments comprise no burn, annual, biennial, triennial, quadrennial and sexennial burns. From this trial a study was conducted to investigate long term effect of burning frequency on species and soil seed bank diversity. Two 100 m line transects located 25 m apart were laid within each plot, and the herbaceous and woody species were identified and recorded along the line transects. Relative abundances (%) for each species were calculated for each treatment. Soil samples were collected at an interval of 13.3 m along the line transects. The samples were placed in paper bags and kept for use in a germination experiment. The seedling emergence germination method was used in the glasshouse to determine emerging seedlings, pots were filled with Hygromix growth medium and the soils from the fire trials 12 X 6 = 72 were spread on top. Soil from the control plots were also pre-treated with heat, smoke and the combination of heat and smoke. The experiment started in January 2010 and was terminated in April 2010. The Shannon-Weaver Diversity Index was used to determine species diversity for standing vegetation and germinated seedlings. Data were tested for normality and species abundances were transformed. Analysis of Variance (ANOVA) was applied to test treatment effects on geminated seedlings, species abundance and diversity at α = 0.05 significance level. Significant differences between treatment means were determined by post v hoc tests using Fischer‟s Least Significant Difference test at α = 0.05. The Pearson Moment Correlation test was used to test the relationship between vegetation and soil seed banks. Treatments had significant effects on herbaceous, woody species abundance and diversity (P < 0.05), but there was no significant treatment effect on soil seed bank diversity and on pre-germination treatments (P > 0.05). The annual, biennial and triennial burns were dominated by Themeda triandra while the quadrennial, sexennial and the control treatments were dominated by Sporobolus fimbriatus and Melica decumbens. A. karroo dominated the woody component across all treatments, but it did not change in abundance. S. fimbriatus was the most abundant in the soil seed bank across all the treatments and also in all pre-germination treatments. Species diversity was high in standing vegetation in the quadrennial, sexennial and the control treatments. There was no significant correlation between the standing vegetation and soil seed bank diversities (P > 0.05). Based on these findings it is apparent that fire can change vegetation in an area to be dominated by fire tolerant or fire intolerant species. Fire frequency, heat and smoke affects soil seed banks to a lesser extent in the False Thornveld. For the management of the False Thornveld of the Eastern Cape, less frequent burning is recommended as it increases aboveground species diversity.
- Full Text:
- Date Issued: 2011
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:
- Date Issued: 2011
- 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:
- Date Issued: 2011
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:
- Date Issued: 2011
- 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:
- Date Issued: 2011