The nature of geometry instruction and observed learning-outcomes opportunities in Nigerian and South African high schools:
- Atebe, Humphrey U, Schäfer, Marc
- Authors: Atebe, Humphrey U , Schäfer, Marc
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140919 , vital:37929 , DOI: 10.1080/10288457.2011.10740712
- Description: The purpose of this qualitative case study involving six secondary school teachers was to obtain insight into how geometry is taught in selected Nigerian and South African high schools. It also aimed, by making use of the van Hiele model of geometry instruction, to elucidate what possible learning opportunities observed instructional methods could offer learners in the subject. The sample comprised three mathematics teachers from Nigeria and three mathematics teachers from South Africa, all of whom were selected using purposive sampling techniques. Instructional activities in six geometry classrooms were recorded on videotape. The van Hiele learning phases provided the framework for data analysis. The findings of this study indicate that observed teaching methods in geometry classrooms in the participating schools offer learners scant opportunity to learn geometry.
- Full Text:
- Date Issued: 2013
- Authors: Atebe, Humphrey U , Schäfer, Marc
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140919 , vital:37929 , DOI: 10.1080/10288457.2011.10740712
- Description: The purpose of this qualitative case study involving six secondary school teachers was to obtain insight into how geometry is taught in selected Nigerian and South African high schools. It also aimed, by making use of the van Hiele model of geometry instruction, to elucidate what possible learning opportunities observed instructional methods could offer learners in the subject. The sample comprised three mathematics teachers from Nigeria and three mathematics teachers from South Africa, all of whom were selected using purposive sampling techniques. Instructional activities in six geometry classrooms were recorded on videotape. The van Hiele learning phases provided the framework for data analysis. The findings of this study indicate that observed teaching methods in geometry classrooms in the participating schools offer learners scant opportunity to learn geometry.
- Full Text:
- Date Issued: 2013
“As soon as the four sides are all equal, then the angles must be 90° each”: children's misconceptions in geometry
- Atebe, Humphrey U, Schäfer, Marc
- Authors: Atebe, Humphrey U , Schäfer, Marc
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140983 , vital:37934 , DOI: 10.1080/10288457.2008.10740634
- Description: This study describes Nigerian and South African students' conceptual understanding in high school geometry based on the van Hiele model of geometric thinking levels. The study further highlights students' misconceptions in school geometry. Concepts of triangles and quadrilaterals were investigated among 36 mathematics learners drawn from grades 10 through 12 who participated in this study. The tasks included identifying and naming shapes, sorting of shapes, stating the properties of shapes, defining of shapes and establishing class inclusions of shapes. The results indicated that many Nigerian and South African high school learners in Grade 10, 11 and 12 hold a number of misconceptions about geometric concepts of triangles and quadrilaterals.
- Full Text:
- Date Issued: 2013
- Authors: Atebe, Humphrey U , Schäfer, Marc
- Date: 2013
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140983 , vital:37934 , DOI: 10.1080/10288457.2008.10740634
- Description: This study describes Nigerian and South African students' conceptual understanding in high school geometry based on the van Hiele model of geometric thinking levels. The study further highlights students' misconceptions in school geometry. Concepts of triangles and quadrilaterals were investigated among 36 mathematics learners drawn from grades 10 through 12 who participated in this study. The tasks included identifying and naming shapes, sorting of shapes, stating the properties of shapes, defining of shapes and establishing class inclusions of shapes. The results indicated that many Nigerian and South African high school learners in Grade 10, 11 and 12 hold a number of misconceptions about geometric concepts of triangles and quadrilaterals.
- Full Text:
- Date Issued: 2013
Mathematics teachers' experiences of designing and implementing a circle geometry teaching programme using the van Hiele phases of instruction as a conceptual framework: a Namibian case study
- Authors: Dongwi, Beata Lididimikeni
- Date: 2013
- Subjects: Geometry -- Study and teaching (Secondary) -- Namibia Mathematics -- Study and teaching -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1412 , http://hdl.handle.net/10962/d1003133
- Description: The aim of this case study was to examine, analyze and report on the findings of the experiences of selected mathematics teachers when they used the van Hiele phases of instruction in designing and implementing a Grade 11 circle geometry teaching programme. The sample consisted of three selected mathematics teachers from the school where the researcher teaches. This school is located in the Oshikoto Education Region in Namibia. The school serves a multicultural group of 759 learners from a middle-class economic background. The site and participants were selected conveniently as the researcher had unrestricted access to both the facilities and the participants. This research takes the form of a case study and is underpinned by the interpretive paradigm. Data for this research was collected using a variety of techniques such as interviews, classroom observation and document analysis. This facilitated easy triangulation of the data. The findings of this research make four claims with regard to the experiences of the mathematics teachers with designing and implementing the circle geometry teaching programme using the five van Hiele phases of instruction as a conceptual framework. The findings revealed that firstly, all three participating mathematics teachers used and implemented all the five van Hiele phases of instruction in their lessons I observed. Secondly, the teachers navigated quite freely from one phase of instruction to the next, but also returned to the earlier phases for clarification and reinforcement in their teaching. Thirdly, the teachers saw the phases of instruction as a good pedagogical tool or template for planning and presenting lessons. Fourthly, the majority of the learners followed the instructions and seemed to obtain the answers faster than expected. The lesson presentations were lively and both teachers and learners communicated at length to discover angle properties of circles while developing and nurturing the technical language of geometry.
- Full Text:
- Date Issued: 2013
- Authors: Dongwi, Beata Lididimikeni
- Date: 2013
- Subjects: Geometry -- Study and teaching (Secondary) -- Namibia Mathematics -- Study and teaching -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1412 , http://hdl.handle.net/10962/d1003133
- Description: The aim of this case study was to examine, analyze and report on the findings of the experiences of selected mathematics teachers when they used the van Hiele phases of instruction in designing and implementing a Grade 11 circle geometry teaching programme. The sample consisted of three selected mathematics teachers from the school where the researcher teaches. This school is located in the Oshikoto Education Region in Namibia. The school serves a multicultural group of 759 learners from a middle-class economic background. The site and participants were selected conveniently as the researcher had unrestricted access to both the facilities and the participants. This research takes the form of a case study and is underpinned by the interpretive paradigm. Data for this research was collected using a variety of techniques such as interviews, classroom observation and document analysis. This facilitated easy triangulation of the data. The findings of this research make four claims with regard to the experiences of the mathematics teachers with designing and implementing the circle geometry teaching programme using the five van Hiele phases of instruction as a conceptual framework. The findings revealed that firstly, all three participating mathematics teachers used and implemented all the five van Hiele phases of instruction in their lessons I observed. Secondly, the teachers navigated quite freely from one phase of instruction to the next, but also returned to the earlier phases for clarification and reinforcement in their teaching. Thirdly, the teachers saw the phases of instruction as a good pedagogical tool or template for planning and presenting lessons. Fourthly, the majority of the learners followed the instructions and seemed to obtain the answers faster than expected. The lesson presentations were lively and both teachers and learners communicated at length to discover angle properties of circles while developing and nurturing the technical language of geometry.
- Full Text:
- Date Issued: 2013
Application of lie group analysis to mathematical models in epidemiology
- Authors: Otieno, Andrew Alex Omondi
- Date: 2013
- Subjects: Epidemiology -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:18486 , http://hdl.handle.net/11260/100
- Description: Lie group analysis is arguably the most systematic vehicle for finding exact solutions of differential equations. Using this approach one has at one's disposal a variety of algorithms that make the solution process of many differential equations algorithmic. Vital properties of a given differential equation can often be inferred from the symmetries admitted by the equation. However, Lie group analysis has not enjoyed wide-spread application to systems of first-order ordinary differential equations. This is because such systems typically admit an infinite number of Lie point symmetries, and there is no systematic way to find even a single nontrivial one-dimensional Lie symmetry algebra. In the few applications available, the approach has been to circumvent the problem by transforming a given system of first-order ordinary differential equations into one in which at least one of the equations is of order two or greater. It is therefore fair to say that the full power of Lie group analysis has not been sufficiently harnessed in the solution of systems of first-order ordinary differential equations. In this dissertation we review some applications of Lie group analysis to systems of first order ordinary differential equations. We shed light on the integration procedure for first-order systems of ordinary differential equations admitting a solvable Lie algebra. We do this via instructive examples drawn from mathematical epidemiology models. In particular we revisit the work of Nucci and Torrisi [54] and improve the exposition of the Lie-symmetry-inspired solution of a mathematical model which describes a HIV transmission. To aid implementation of the integration strategy for systems of ordinary differential equations, we have developed ad-hoc routines for finding particular types of admitted symmetries and checking if a given symmetry is indeed admitted by a system of ordinary differential equations.
- Full Text:
- Date Issued: 2013
- Authors: Otieno, Andrew Alex Omondi
- Date: 2013
- Subjects: Epidemiology -- Mathematical models
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:18486 , http://hdl.handle.net/11260/100
- Description: Lie group analysis is arguably the most systematic vehicle for finding exact solutions of differential equations. Using this approach one has at one's disposal a variety of algorithms that make the solution process of many differential equations algorithmic. Vital properties of a given differential equation can often be inferred from the symmetries admitted by the equation. However, Lie group analysis has not enjoyed wide-spread application to systems of first-order ordinary differential equations. This is because such systems typically admit an infinite number of Lie point symmetries, and there is no systematic way to find even a single nontrivial one-dimensional Lie symmetry algebra. In the few applications available, the approach has been to circumvent the problem by transforming a given system of first-order ordinary differential equations into one in which at least one of the equations is of order two or greater. It is therefore fair to say that the full power of Lie group analysis has not been sufficiently harnessed in the solution of systems of first-order ordinary differential equations. In this dissertation we review some applications of Lie group analysis to systems of first order ordinary differential equations. We shed light on the integration procedure for first-order systems of ordinary differential equations admitting a solvable Lie algebra. We do this via instructive examples drawn from mathematical epidemiology models. In particular we revisit the work of Nucci and Torrisi [54] and improve the exposition of the Lie-symmetry-inspired solution of a mathematical model which describes a HIV transmission. To aid implementation of the integration strategy for systems of ordinary differential equations, we have developed ad-hoc routines for finding particular types of admitted symmetries and checking if a given symmetry is indeed admitted by a system of ordinary differential equations.
- Full Text:
- Date Issued: 2013
A Comparative study of two copper(II) based metal-organic frameworks : Cu2¼(OH)½B4C•8H2O and Cu2Na(OH)B4C•7H2O
- Authors: Coombes, Matthew
- Date: 2013
- Subjects: Copper , Organometallic compounds , Supramolecular organometallic chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4533 , http://hdl.handle.net/10962/d1016245
- Description: This study focussed on two copper(II)-containing metal-organic frameworks (MOFs): Cu2Na(OH)B4C•7H2O and Cu2¼(OH)½B4C•8H2O (B4C = 1,2,4,5- benzenetetracarboxylate). They are both covalent, three-dimensional metalorganic framework polymers containing voids filled with water molecules. Both were characterised by elemental analysis, infrared spectroscopy, X-ray powder diffractometry (both in situ and regular), thermogravimetric analysis, differential scanning calorimetry and X-ray photoelectron spectroscopy. These two MOFs are essentially identical, with the only difference being the substitution of sodium by copper at every 4th site (disordered throughout the crystal). The guest inclusion properties of both MOFs were studied and compared. Although both structures collapse on dehydration, it was observed that Cu2Na(OH)B4C•7H2O is able to take up signifcant amounts of water, methanol and ethanol. All these processes are fully reversible. Car-Parrinello molecular dynamics studies suggest that it is a strong interaction between the oxygen atoms on these molecules with the sodium cation of the MOF that is responsible for this signifcant uptake. In contrast, Cu2¼ (OH)½ B4C•8H2O, the MOF without a sodium cation, did not demonstrate any methanol or ethanol uptake, but was able to take up some water. The uptake of water, however, is not a fully reversible process. The absence of sodium likely results in insuffcient energy to draw methanol and ethanol into the framework, while a subtle rotation of a carboxylate group on dehydration decreases the ability of the framework to form hydrogen bonds, thus reducing the ability to take up water. A series of hydrothermal syntheses were performed in order to develop a method of synthesis superior to the current gel-based synthesis that requires several months and has poor yields. The hydrothermal products were characterized by elemental analysis, infrared spectroscopy, X-ray powder diffractometry, thermogravimetric analysis and differential scanning calorimetry. It was shown that the MOF Cu2Na(OH)B4C•7H2O may be synthesised in almost 100% yield by using a temperature of 120°C over a period of 72 hours. It was not possible to synthesise Cu2¼ (OH)½ B4C•8H2O in a 100% yield - it was only obtained as a minor product.
- Full Text:
- Date Issued: 2013
- Authors: Coombes, Matthew
- Date: 2013
- Subjects: Copper , Organometallic compounds , Supramolecular organometallic chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4533 , http://hdl.handle.net/10962/d1016245
- Description: This study focussed on two copper(II)-containing metal-organic frameworks (MOFs): Cu2Na(OH)B4C•7H2O and Cu2¼(OH)½B4C•8H2O (B4C = 1,2,4,5- benzenetetracarboxylate). They are both covalent, three-dimensional metalorganic framework polymers containing voids filled with water molecules. Both were characterised by elemental analysis, infrared spectroscopy, X-ray powder diffractometry (both in situ and regular), thermogravimetric analysis, differential scanning calorimetry and X-ray photoelectron spectroscopy. These two MOFs are essentially identical, with the only difference being the substitution of sodium by copper at every 4th site (disordered throughout the crystal). The guest inclusion properties of both MOFs were studied and compared. Although both structures collapse on dehydration, it was observed that Cu2Na(OH)B4C•7H2O is able to take up signifcant amounts of water, methanol and ethanol. All these processes are fully reversible. Car-Parrinello molecular dynamics studies suggest that it is a strong interaction between the oxygen atoms on these molecules with the sodium cation of the MOF that is responsible for this signifcant uptake. In contrast, Cu2¼ (OH)½ B4C•8H2O, the MOF without a sodium cation, did not demonstrate any methanol or ethanol uptake, but was able to take up some water. The uptake of water, however, is not a fully reversible process. The absence of sodium likely results in insuffcient energy to draw methanol and ethanol into the framework, while a subtle rotation of a carboxylate group on dehydration decreases the ability of the framework to form hydrogen bonds, thus reducing the ability to take up water. A series of hydrothermal syntheses were performed in order to develop a method of synthesis superior to the current gel-based synthesis that requires several months and has poor yields. The hydrothermal products were characterized by elemental analysis, infrared spectroscopy, X-ray powder diffractometry, thermogravimetric analysis and differential scanning calorimetry. It was shown that the MOF Cu2Na(OH)B4C•7H2O may be synthesised in almost 100% yield by using a temperature of 120°C over a period of 72 hours. It was not possible to synthesise Cu2¼ (OH)½ B4C•8H2O in a 100% yield - it was only obtained as a minor product.
- Full Text:
- Date Issued: 2013
Synthesis and characterisation of oxorhenium(V) and tricarbonylrhenium(I) complexes with biologically active N, O and N, S-Donor ligands
- Authors: Mukiza, Janvier
- Date: 2013
- Subjects: Rhenium , Rhenium compounds , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10437 , http://hdl.handle.net/10948/d1020769
- Description: This study investigated the synthesis of rhenium(I) and rhenium(V) complexes with a variety of multidentate NS, NSO, NO and SO-donor ligands. It also investigated the synthesis of dinuclear dihalogeno- and trihalogeno-bridged rhenium(I) complexes based on the fac-[Re(CO)3]+ core. The reactions of hydrated folic acid with [Re(CO)5X] (X = Cl, Br) were studied, and the complexes [Re(CO)3(H2O)3]+[Re2(μ-X)3CO)6]−.5H2O [X= Br (1), Cl(2)] were isolated. The reaction of orotic acid potassium salt [Re(CO)5Br] was performed, and the complex [Re2(μ-Br)2(CO)8] was isolated. The reaction of bis(piperidin-1- yl)methanone with [Re(CO)5Cl] followed by recrystallisation of the resulting precipitate in dichloromethane/acetontrile resulted in the complex [Re2(μ- Cl)2(CO)6(MeCN)2]. The X-ray crystal structures show that all these complexes display a distorted octahedral geometry around the central rhenium atoms. The reactions of aroylhydrazone-based ligands such as 3-((pyridin- 2yl)methyleneamino)-2,3-dihydro-2-pyridin-2yl)quinazolin-4-(1H)-one (Hppq) and N-(di(pyridin-2-yl)methylene)benzohydrazide (Hdpmb) with [Re(CO)5Cl] were studied and led to the formation of the complexes [Re(CO)3Cl(Hdpmb)] and [Re(CO)3Cl(Hppq)]. The Hdpmb and Hppq coordinated to the fac-[Re(CO)3]+ core as neutral bidentate chalates via the pyridinic nitrogens (for Hdpmb) and via imino and pyridinic nitrogens for Hppq. The X-ray crystal structures show that the geometry around the rhenium in both complexes is a distorted octahedral. The treatment of the dithizone (H2dz) ligand with rhenium(V) precursors containing a triphenylphosphine group (PPh3) led to the decomposition of dithizone. The decomposition product reacted with the triphenylphosphine group and generated a new ligand triphenylphosphazeno-N-phenylmethanethiohydrazide (H2L). The reaction of trans-[ReOX3(PPh3)2] (X = Cl, Br) with dithizone (H2dz) led to the complex [ReO(dz)2][ReO(HL)2]. The reaction of trans-[ReOI2(OEt)(PPh3)2] with H2dz led to the same product. The reaction of cis-[ReO2I(PPh3)2] with H2dz in methanol led to [ReO(dz)2][ReO(HL)2](MeOH)2 in which methanol bonded to HLvia hydrogen bonds. The H2dz was doubly deprotonated and coordinated to the [ReO]3+ moiety via a thiolate sulfur and deprotonated hydrazinic nitrogen to yield [ReO(dz)2]−, while the H2L was singly deprotonated and coordinated to [ReO]3+ moiety via the neutral sulfur atom and deprotonated hydrazinic nitrogen to yield [ReO(HL)2]+. The X-ray crystal structure show that in both [ReO(HL)2]+ and [ReO(dz)2]−, the rhenium atoms are five-coordinated and adopt a distorted squarebased pyramidal geometry. The reaction of thiosemicarbazones such as salcylidene-4- phenylthiosemicarbazide (H3salpt) with cis-[ReO2I(PPh3)2] was investigated and led to the complex [ReO(Hsalpt)(H2salpt)]. The X-ray study reveals that Hsalpt is present as a tridentate chelate coordinating via the thiolate sulfur, imino nitrogen and phenolic oxygen, while H2salpt coordinates as a bidentate chelate via the thiolate sulfur and imino nitrogen atoms. The geometry around rhenium is distorted octahedral. The coordination mode of the benzoylthiourea derivatives 4-tert-butyl-N- (diphenylcarbamothioyl)benzamide (Htpb) and N-(diethylcarbamothioyl)benzamide (Heb) to the [Re2O3]4+ and fac-[Re(CO)3]+ cores were investigated. The reaction of [Re(CO)5Cl] in presence of sodium acetate with Htpb led to the dimeric complex [Re(CO)3(tpb)]2 in which the tpb coordinated to the fac-[Re(CO)3]+ core via the ketonic oxygen and bridging thiolate sulfur. The same reaction with Heb led to the monomeric complex [Re(CO)3(eb)(Heb)], in which the eb coordinates to the fac-[Re(CO)3]+core via thiolate sulfur and ketonic oxygen with Heb binding via the neutral sulfur atom. The reaction of Heb with cis-[ReO2I(PPh3)2] at room temperature with excess of sodium acetate led to the dimeric complex (μ-O)[ReO(eb)2]2 in which Heb is present as a monoanionic (deprotonated) bidentate with coordination through the thiolate sulfur and ketonic oxygen.
- Full Text:
- Date Issued: 2013
- Authors: Mukiza, Janvier
- Date: 2013
- Subjects: Rhenium , Rhenium compounds , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10437 , http://hdl.handle.net/10948/d1020769
- Description: This study investigated the synthesis of rhenium(I) and rhenium(V) complexes with a variety of multidentate NS, NSO, NO and SO-donor ligands. It also investigated the synthesis of dinuclear dihalogeno- and trihalogeno-bridged rhenium(I) complexes based on the fac-[Re(CO)3]+ core. The reactions of hydrated folic acid with [Re(CO)5X] (X = Cl, Br) were studied, and the complexes [Re(CO)3(H2O)3]+[Re2(μ-X)3CO)6]−.5H2O [X= Br (1), Cl(2)] were isolated. The reaction of orotic acid potassium salt [Re(CO)5Br] was performed, and the complex [Re2(μ-Br)2(CO)8] was isolated. The reaction of bis(piperidin-1- yl)methanone with [Re(CO)5Cl] followed by recrystallisation of the resulting precipitate in dichloromethane/acetontrile resulted in the complex [Re2(μ- Cl)2(CO)6(MeCN)2]. The X-ray crystal structures show that all these complexes display a distorted octahedral geometry around the central rhenium atoms. The reactions of aroylhydrazone-based ligands such as 3-((pyridin- 2yl)methyleneamino)-2,3-dihydro-2-pyridin-2yl)quinazolin-4-(1H)-one (Hppq) and N-(di(pyridin-2-yl)methylene)benzohydrazide (Hdpmb) with [Re(CO)5Cl] were studied and led to the formation of the complexes [Re(CO)3Cl(Hdpmb)] and [Re(CO)3Cl(Hppq)]. The Hdpmb and Hppq coordinated to the fac-[Re(CO)3]+ core as neutral bidentate chalates via the pyridinic nitrogens (for Hdpmb) and via imino and pyridinic nitrogens for Hppq. The X-ray crystal structures show that the geometry around the rhenium in both complexes is a distorted octahedral. The treatment of the dithizone (H2dz) ligand with rhenium(V) precursors containing a triphenylphosphine group (PPh3) led to the decomposition of dithizone. The decomposition product reacted with the triphenylphosphine group and generated a new ligand triphenylphosphazeno-N-phenylmethanethiohydrazide (H2L). The reaction of trans-[ReOX3(PPh3)2] (X = Cl, Br) with dithizone (H2dz) led to the complex [ReO(dz)2][ReO(HL)2]. The reaction of trans-[ReOI2(OEt)(PPh3)2] with H2dz led to the same product. The reaction of cis-[ReO2I(PPh3)2] with H2dz in methanol led to [ReO(dz)2][ReO(HL)2](MeOH)2 in which methanol bonded to HLvia hydrogen bonds. The H2dz was doubly deprotonated and coordinated to the [ReO]3+ moiety via a thiolate sulfur and deprotonated hydrazinic nitrogen to yield [ReO(dz)2]−, while the H2L was singly deprotonated and coordinated to [ReO]3+ moiety via the neutral sulfur atom and deprotonated hydrazinic nitrogen to yield [ReO(HL)2]+. The X-ray crystal structure show that in both [ReO(HL)2]+ and [ReO(dz)2]−, the rhenium atoms are five-coordinated and adopt a distorted squarebased pyramidal geometry. The reaction of thiosemicarbazones such as salcylidene-4- phenylthiosemicarbazide (H3salpt) with cis-[ReO2I(PPh3)2] was investigated and led to the complex [ReO(Hsalpt)(H2salpt)]. The X-ray study reveals that Hsalpt is present as a tridentate chelate coordinating via the thiolate sulfur, imino nitrogen and phenolic oxygen, while H2salpt coordinates as a bidentate chelate via the thiolate sulfur and imino nitrogen atoms. The geometry around rhenium is distorted octahedral. The coordination mode of the benzoylthiourea derivatives 4-tert-butyl-N- (diphenylcarbamothioyl)benzamide (Htpb) and N-(diethylcarbamothioyl)benzamide (Heb) to the [Re2O3]4+ and fac-[Re(CO)3]+ cores were investigated. The reaction of [Re(CO)5Cl] in presence of sodium acetate with Htpb led to the dimeric complex [Re(CO)3(tpb)]2 in which the tpb coordinated to the fac-[Re(CO)3]+ core via the ketonic oxygen and bridging thiolate sulfur. The same reaction with Heb led to the monomeric complex [Re(CO)3(eb)(Heb)], in which the eb coordinates to the fac-[Re(CO)3]+core via thiolate sulfur and ketonic oxygen with Heb binding via the neutral sulfur atom. The reaction of Heb with cis-[ReO2I(PPh3)2] at room temperature with excess of sodium acetate led to the dimeric complex (μ-O)[ReO(eb)2]2 in which Heb is present as a monoanionic (deprotonated) bidentate with coordination through the thiolate sulfur and ketonic oxygen.
- Full Text:
- Date Issued: 2013
Fixed points of single-valued and multi-valued mappings with applications
- Authors: Stofile, Simfumene
- Date: 2013
- Subjects: Fixed point theory Mappings (Mathematics) Coincidence theory (Mathematics) Metric spaces Uniform spaces Set-valued maps
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5397 , http://hdl.handle.net/10962/d1002960
- Description: The relationship between the convergence of a sequence of self mappings of a metric space and their fixed points, known as the stability (or continuity) of fixed points has been of continuing interest and widely studied in fixed point theory. In this thesis we study the stability of common fixed points in a Hausdorff uniform space whose uniformity is generated by a family of pseudometrics, by using some general notations of convergence. These results are then extended to 2-metric spaces due to S. Gähler. In addition, a well-known theorem of T. Suzuki that generalized the Banach Contraction Principle is also extended to 2-metric spaces and applied to obtain a coincidence theorem for a pair of mappings on an arbitrary set with values in a 2-metric space. Further, we prove the existence of coincidence and fixed points of Ćirić type weakly generalized contractions in metric spaces. Subsequently, the above result is utilized to discuss applications to the convergence of modified Mann and Ishikawa iterations in a convex metric space. Finally, we obtain coincidence, fixed and stationary point results for multi-valued and hybrid pairs of mappings on a metric space.
- Full Text:
- Date Issued: 2013
- Authors: Stofile, Simfumene
- Date: 2013
- Subjects: Fixed point theory Mappings (Mathematics) Coincidence theory (Mathematics) Metric spaces Uniform spaces Set-valued maps
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5397 , http://hdl.handle.net/10962/d1002960
- Description: The relationship between the convergence of a sequence of self mappings of a metric space and their fixed points, known as the stability (or continuity) of fixed points has been of continuing interest and widely studied in fixed point theory. In this thesis we study the stability of common fixed points in a Hausdorff uniform space whose uniformity is generated by a family of pseudometrics, by using some general notations of convergence. These results are then extended to 2-metric spaces due to S. Gähler. In addition, a well-known theorem of T. Suzuki that generalized the Banach Contraction Principle is also extended to 2-metric spaces and applied to obtain a coincidence theorem for a pair of mappings on an arbitrary set with values in a 2-metric space. Further, we prove the existence of coincidence and fixed points of Ćirić type weakly generalized contractions in metric spaces. Subsequently, the above result is utilized to discuss applications to the convergence of modified Mann and Ishikawa iterations in a convex metric space. Finally, we obtain coincidence, fixed and stationary point results for multi-valued and hybrid pairs of mappings on a metric space.
- Full Text:
- Date Issued: 2013
Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands
- Authors: Habarurema, Gratien
- Date: 2013
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10441 , http://hdl.handle.net/10948/d1020952
- Description: This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the synthesis of tridentate, tetradentate and pentadentate Schiff bases ligands derived from the condensation reactions of benzaldehyde with different primary amines. The structures of these Schiff bases and their complexes were confirmed by using physical characterization methods, namely melting points, UV-Visible, UV-emission, 1H NMR and IR spectroscopy, X-ray diffractometry and elemental analysis. To further understand the coordination chemistry of rhenium, the prepared diiminediphenol N2O2-donor Schiff base ligand N N′-o-phenylene-bis(salicylaldimine) (H2salphen) was reacted with trans-[ReOCl3(PPh3)2] to yield cis-[ReCl2(ophsal)(PPh3)], whereas its reaction with trans-[ReOBr3(PPh3)2] resulted in the formation of the cis-[ReBr2(aphsal)(PPh3)].2CH3CN complex. In the above complexes the H2salphen ligand was cleaved leading to the coordinated tridentate ophsal NO2- and aphsal N2O-donor ligands. The reaction of H3aphsal with trans-[ReOBr3(PPh3)2] in toluene led to an unexpected compound, trans- [{[ReBr(aphsal)(PPh3)2]Br}{[ReBr(aphsal)(PPh3)2](ReO4)}] with an imido [ReNR]3+core. The ligand aphsal was coordinated tridentately with the doubly deprotonated amino nitrogen leading to Re(V)-imido complexes. The reaction of 2-((Z)-(2-aminoethylimino)methyl)phenol (H3amphol) with [Re(CO)5Cl] led to the rhenium(I) product fac-[Re(CO)3(H3amphol)] with H3amphol coordinated as a monoanionic tridentate chelate through its phenolate oxygen and amino nitrogen atoms. The X-ray crystal structures showed that all complexes display a distorted octahedral geometry around the central rhenium atom. The reaction of 2,6-bis(2-hydroxyphenylimino)pyridine (H2hpp) with cis-[ReO2I(PPh3)2] resulted in the reduced Re(III) product trans-[Re(hpp)(PPh3)2]I, while trans-[Re(hpp)(PPh3)2](ReO4) was isolated from its reaction with trans-[ReOCl3(PPh3)2]. The H2hpp ligand acts as a pentadentate N3O2-donor ligand where the two phenolic protons undergo deprotonation and its three nitrogens act as neutral donor atoms. Both compounds resulted from a disproportionation reaction characterized by the produced perrhenate counter-ion. The complex fac-[Re(CO)3(H2hpp)Cl] was prepared from [Re(CO)5Cl] and H2hpp in toluene. The H2hpp ligand acted as a neutral bidentate N,N-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, two neutral nitrogen atoms and a chloride ligand. The reactions of the potentially tetradentate ligand N,N'-ethylenebis(salicylideneimine) (H2salen) with different rhenium(V) precursors resulted in the formation of two dimeric oxorhenium (V) compounds. In the reaction of H2salen with trans-[ReOCl3(PPh3)2] in ethanol, the highly unusual distorted dimeric complex (μ-salen)[ReOCl2(PPh3)]2 was isolated, in which salen2- is coordinated as a tetradentate to two oxorhenium(V) centres, and salen2- is present as a bidentate monoanionic ligand on each rhenium center. The reaction of cis- [ReO2I(PPh3)2] with H2salen led to the formation of the neutral dimeric oxorhenium(V) complex (μ-O)[ReO(salen)]2 in which the tetradentate chelate salen acts as a tetradentate dianionic ligand through its phenolate oxygens and nitrogen atoms of the azomethine groups. In its reaction with H2hmp the compound (μ-O)[ReO(hmp)]2 was isolated. In this product the pentadentate ligand H2hmp coordinated as tetradentate via its phenolic oxygen and nitrogen atoms. The reaction of the potentially tetradentate N1,N2-bis(aminobenzylidene)-1,2-ethylenediamine (H2amben) with trans-[ReOCl3(PPh3)2] led to the formation of the monocationic square-pyramidal complex salt [ReO(amben)](ReO4.
- Full Text:
- Date Issued: 2013
- Authors: Habarurema, Gratien
- Date: 2013
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10441 , http://hdl.handle.net/10948/d1020952
- Description: This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the synthesis of tridentate, tetradentate and pentadentate Schiff bases ligands derived from the condensation reactions of benzaldehyde with different primary amines. The structures of these Schiff bases and their complexes were confirmed by using physical characterization methods, namely melting points, UV-Visible, UV-emission, 1H NMR and IR spectroscopy, X-ray diffractometry and elemental analysis. To further understand the coordination chemistry of rhenium, the prepared diiminediphenol N2O2-donor Schiff base ligand N N′-o-phenylene-bis(salicylaldimine) (H2salphen) was reacted with trans-[ReOCl3(PPh3)2] to yield cis-[ReCl2(ophsal)(PPh3)], whereas its reaction with trans-[ReOBr3(PPh3)2] resulted in the formation of the cis-[ReBr2(aphsal)(PPh3)].2CH3CN complex. In the above complexes the H2salphen ligand was cleaved leading to the coordinated tridentate ophsal NO2- and aphsal N2O-donor ligands. The reaction of H3aphsal with trans-[ReOBr3(PPh3)2] in toluene led to an unexpected compound, trans- [{[ReBr(aphsal)(PPh3)2]Br}{[ReBr(aphsal)(PPh3)2](ReO4)}] with an imido [ReNR]3+core. The ligand aphsal was coordinated tridentately with the doubly deprotonated amino nitrogen leading to Re(V)-imido complexes. The reaction of 2-((Z)-(2-aminoethylimino)methyl)phenol (H3amphol) with [Re(CO)5Cl] led to the rhenium(I) product fac-[Re(CO)3(H3amphol)] with H3amphol coordinated as a monoanionic tridentate chelate through its phenolate oxygen and amino nitrogen atoms. The X-ray crystal structures showed that all complexes display a distorted octahedral geometry around the central rhenium atom. The reaction of 2,6-bis(2-hydroxyphenylimino)pyridine (H2hpp) with cis-[ReO2I(PPh3)2] resulted in the reduced Re(III) product trans-[Re(hpp)(PPh3)2]I, while trans-[Re(hpp)(PPh3)2](ReO4) was isolated from its reaction with trans-[ReOCl3(PPh3)2]. The H2hpp ligand acts as a pentadentate N3O2-donor ligand where the two phenolic protons undergo deprotonation and its three nitrogens act as neutral donor atoms. Both compounds resulted from a disproportionation reaction characterized by the produced perrhenate counter-ion. The complex fac-[Re(CO)3(H2hpp)Cl] was prepared from [Re(CO)5Cl] and H2hpp in toluene. The H2hpp ligand acted as a neutral bidentate N,N-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, two neutral nitrogen atoms and a chloride ligand. The reactions of the potentially tetradentate ligand N,N'-ethylenebis(salicylideneimine) (H2salen) with different rhenium(V) precursors resulted in the formation of two dimeric oxorhenium (V) compounds. In the reaction of H2salen with trans-[ReOCl3(PPh3)2] in ethanol, the highly unusual distorted dimeric complex (μ-salen)[ReOCl2(PPh3)]2 was isolated, in which salen2- is coordinated as a tetradentate to two oxorhenium(V) centres, and salen2- is present as a bidentate monoanionic ligand on each rhenium center. The reaction of cis- [ReO2I(PPh3)2] with H2salen led to the formation of the neutral dimeric oxorhenium(V) complex (μ-O)[ReO(salen)]2 in which the tetradentate chelate salen acts as a tetradentate dianionic ligand through its phenolate oxygens and nitrogen atoms of the azomethine groups. In its reaction with H2hmp the compound (μ-O)[ReO(hmp)]2 was isolated. In this product the pentadentate ligand H2hmp coordinated as tetradentate via its phenolic oxygen and nitrogen atoms. The reaction of the potentially tetradentate N1,N2-bis(aminobenzylidene)-1,2-ethylenediamine (H2amben) with trans-[ReOCl3(PPh3)2] led to the formation of the monocationic square-pyramidal complex salt [ReO(amben)](ReO4.
- Full Text:
- Date Issued: 2013
Photophysicochemical properties of aluminium phthalocyanine-platinum conjugates
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
The restoration of an alien-invaded riparian zone in grassy fynbos, South Africa
- Authors: Fourie, Saskia
- Date: 2013
- Subjects: Fynbos ecology -- South Africa Riparian ecology -- South Africa Riparian restoration -- South Africa Alien plants -- South Africa Invasive plants -- South Africa Endemic plants -- South Africa Plants -- Effect of fires on -- South Africa Soil seed banks -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4733 , http://hdl.handle.net/10962/d1003840
- Description: The most recent surveys in South Africa estimate that invasions are still increasing, despite substantial clearing efforts. Riparian systems in South Africa are particularly vulnerable to invasion by woody IAPs. This thesis addresses the restoration of alien‐invaded riparian systems, by investigating the factors that facilitate or constrain spontaneous recovery and influence the trajectories of succession. These factors include invasion history and management history, especially the use of fire. A seedling emergence approach was used to test the presence of a viable pre‐fire seedbank, and the effect of fire on the seed bank. The efficacy of some active restoration interventions was also tested, with the aim to return invasion‐resistant, indigenous vegetation with a structure and function representative of uninvaded sites. The findings of this study indicated the presence of a viable and persistent riparian soil seed bank, even after 30 years of intermtittent invasion as well as two fire cycles under invasion. It shows that the management practice of fell‐and‐burn resulted in high soil temperatures, and that this reduced the indigenous soil seed bank density, especially in the upper soil layer. Clear germination sequences and patterns of emergence over time for different species were observed during this study, with many species exhibiting delayed emergence relative to the timing of the fire event. It is proposed that manipulation of the season of fire could be used to selectively optimise the order of arrival and therefore superior recruitment of some species over others in the Eastern Cape fynbos, and thus alter the trajectories of recovery of vegetation towards a more desired state. Active restoration in the form of indigenous seed and plant additions resulted in a significantly higher indigenous cover after seven months, compared to a control (passive restoration) or restoring with grass. Indigenous cover and composition was also strongly influenced by lateral zonation, and some key guilds and species were missing or present in much lower densities compared to reference sites. Grass restoration significantly suppressed the regeneration of A. longifolia, as well as the regeneration of indigenous species. Biotic resistance can thus be achieved through restoration, and it could be a powerful tool in the management of IAPs, although the deliberate introduction of grass after clearing in fynbos also reduces biodiversity and could have unforeseen consequences to riparian function.
- Full Text:
- Date Issued: 2013
- Authors: Fourie, Saskia
- Date: 2013
- Subjects: Fynbos ecology -- South Africa Riparian ecology -- South Africa Riparian restoration -- South Africa Alien plants -- South Africa Invasive plants -- South Africa Endemic plants -- South Africa Plants -- Effect of fires on -- South Africa Soil seed banks -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4733 , http://hdl.handle.net/10962/d1003840
- Description: The most recent surveys in South Africa estimate that invasions are still increasing, despite substantial clearing efforts. Riparian systems in South Africa are particularly vulnerable to invasion by woody IAPs. This thesis addresses the restoration of alien‐invaded riparian systems, by investigating the factors that facilitate or constrain spontaneous recovery and influence the trajectories of succession. These factors include invasion history and management history, especially the use of fire. A seedling emergence approach was used to test the presence of a viable pre‐fire seedbank, and the effect of fire on the seed bank. The efficacy of some active restoration interventions was also tested, with the aim to return invasion‐resistant, indigenous vegetation with a structure and function representative of uninvaded sites. The findings of this study indicated the presence of a viable and persistent riparian soil seed bank, even after 30 years of intermtittent invasion as well as two fire cycles under invasion. It shows that the management practice of fell‐and‐burn resulted in high soil temperatures, and that this reduced the indigenous soil seed bank density, especially in the upper soil layer. Clear germination sequences and patterns of emergence over time for different species were observed during this study, with many species exhibiting delayed emergence relative to the timing of the fire event. It is proposed that manipulation of the season of fire could be used to selectively optimise the order of arrival and therefore superior recruitment of some species over others in the Eastern Cape fynbos, and thus alter the trajectories of recovery of vegetation towards a more desired state. Active restoration in the form of indigenous seed and plant additions resulted in a significantly higher indigenous cover after seven months, compared to a control (passive restoration) or restoring with grass. Indigenous cover and composition was also strongly influenced by lateral zonation, and some key guilds and species were missing or present in much lower densities compared to reference sites. Grass restoration significantly suppressed the regeneration of A. longifolia, as well as the regeneration of indigenous species. Biotic resistance can thus be achieved through restoration, and it could be a powerful tool in the management of IAPs, although the deliberate introduction of grass after clearing in fynbos also reduces biodiversity and could have unforeseen consequences to riparian function.
- Full Text:
- Date Issued: 2013
Perceptions on ante-mortem welfare, quantitation of pain and pregnancy biomarkers, muscular fibre architecture and quality of Dohne Merino offal
- Authors: Fayemi, Peter Olutope
- Date: 2013
- Subjects: Merino sheep , Slaughtering and slaughter-houses -- By-products , Biochemical markers , Meat -- Quality , Consumers' preferences , Cooking (Variety meats) , Livestock -- Transportation
- Language: English
- Type: Thesis , Doctoral , PhD (Animal Science)
- Identifier: vital:11824 , http://hdl.handle.net/10353/d1007573 , Merino sheep , Slaughtering and slaughter-houses -- By-products , Biochemical markers , Meat -- Quality , Consumers' preferences , Cooking (Variety meats) , Livestock -- Transportation
- Description: Sheep farming is practiced extensively in South Africa for its significant contributions to the livestock, wool and meat industries. The sheep farming sector in the country has approximately 13,800 farmers with commercial and communal sheep farmers making up 58 percent and 42 percent of the entire work force (Directorate of Agricultural Information Services, 2008). An estimate of 28.8 million sheep and flock size ranging between ≤ 50 and ≥ 1800 exist in various South African provinces. Although the national herd size is unevenly distributed provincially most of the herds are found in the Eastern Cape (30 percent) followed by the Northern Cape (25 percent), Free State (20 percent) and the Western Cape (11 percent) respectively (Agriculture, Forestry and Fisheries, 2011). Over twenty indigenous and locally developed sheep breeds are managed where about 69 percent of the land area is available for their grazing nation-wide (Campher et al., 1998; Palmer and Ainslie, 2006). Common among the indigenous breeds are the Afrikaner, Blackhead Persian, Blackhead Speckled Persian, Blinkhaar Ronderib, Damara, Karakul, Namaqua Afrikaner, Pedi, Redhead Persian, Redhead Speckled, Swazi and Zulu. The locally developed breeds include Dorper, Van Rooy and Merinos. The local breeds developed from Merinos consist of the Afrino, Dormer, Dohne Merino and South African mutton Merino (Hammond, 2000; Pranisha, 2004; Hinton, 2006; Sorma et al., 2012). All these sheep breeds are best suited for providing by-products such as wool, meat, hide, milk or a combination of products (Dave and Meadowcroft, 1996; Jensen, 2009). The indigenous and locally developed sheep were bred to meet the growing demand for its by-products (Peters et al., 2010). Expectedly, sheep farmers therefore, make use of the products from these sheep as a means of livelihood and sustenance of a viable local society (Cloete and Olivier, 2010).
- Full Text:
- Date Issued: 2013
- Authors: Fayemi, Peter Olutope
- Date: 2013
- Subjects: Merino sheep , Slaughtering and slaughter-houses -- By-products , Biochemical markers , Meat -- Quality , Consumers' preferences , Cooking (Variety meats) , Livestock -- Transportation
- Language: English
- Type: Thesis , Doctoral , PhD (Animal Science)
- Identifier: vital:11824 , http://hdl.handle.net/10353/d1007573 , Merino sheep , Slaughtering and slaughter-houses -- By-products , Biochemical markers , Meat -- Quality , Consumers' preferences , Cooking (Variety meats) , Livestock -- Transportation
- Description: Sheep farming is practiced extensively in South Africa for its significant contributions to the livestock, wool and meat industries. The sheep farming sector in the country has approximately 13,800 farmers with commercial and communal sheep farmers making up 58 percent and 42 percent of the entire work force (Directorate of Agricultural Information Services, 2008). An estimate of 28.8 million sheep and flock size ranging between ≤ 50 and ≥ 1800 exist in various South African provinces. Although the national herd size is unevenly distributed provincially most of the herds are found in the Eastern Cape (30 percent) followed by the Northern Cape (25 percent), Free State (20 percent) and the Western Cape (11 percent) respectively (Agriculture, Forestry and Fisheries, 2011). Over twenty indigenous and locally developed sheep breeds are managed where about 69 percent of the land area is available for their grazing nation-wide (Campher et al., 1998; Palmer and Ainslie, 2006). Common among the indigenous breeds are the Afrikaner, Blackhead Persian, Blackhead Speckled Persian, Blinkhaar Ronderib, Damara, Karakul, Namaqua Afrikaner, Pedi, Redhead Persian, Redhead Speckled, Swazi and Zulu. The locally developed breeds include Dorper, Van Rooy and Merinos. The local breeds developed from Merinos consist of the Afrino, Dormer, Dohne Merino and South African mutton Merino (Hammond, 2000; Pranisha, 2004; Hinton, 2006; Sorma et al., 2012). All these sheep breeds are best suited for providing by-products such as wool, meat, hide, milk or a combination of products (Dave and Meadowcroft, 1996; Jensen, 2009). The indigenous and locally developed sheep were bred to meet the growing demand for its by-products (Peters et al., 2010). Expectedly, sheep farmers therefore, make use of the products from these sheep as a means of livelihood and sustenance of a viable local society (Cloete and Olivier, 2010).
- Full Text:
- Date Issued: 2013
Synthesis of fluorescent polymers with pendant triazole-substituted coumarin side-chains via a combination of click chemistry and raft-mediated polymerization
- Authors: Wali, Nwabisa Whitney
- Date: 2013
- Subjects: Fluorescent polymers , Polymerization , Macromolecules -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10432 , http://hdl.handle.net/10948/d1020142
- Description: This research project focuses on the synthesis of fluorescent polymers with pendant triazole-substituted coumarin side chain units. Copper(I)-catalyzed Huisgen’s 1,3-dipolar cycloaddition of alkynes with azides to form a 1,2,3-triazole ring, a typical example of “click” reaction, has been utilized for the synthesis of a novel vinyl monomer, 2-oxo-3-(4- vinyl-1H-1,2,3-triazol-1-yl)-2H-chromen-7-yl acetate 62. The monomer and its precursors were synthesised and characterized using 1D- and 2D-NMR and FT-IR. Coumarin-containing triazole polymers were synthesised using free radical polymerization. Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated polymerization was used to synthesise well defined coumarin-containing triazole polymers with moderate PDI values. The polymers were characterised using 1H-NMR and FT-IR. Modelling of the monomer precursor 61 and the monomer 62 at DFT level of approximation provided useful insights into possible conformations adopted by the monomer precursor 61 and the monomer 62. The photophysical properties of the novel monomer and the synthesised polymers were investigated in a polar solvent.
- Full Text:
- Date Issued: 2013
- Authors: Wali, Nwabisa Whitney
- Date: 2013
- Subjects: Fluorescent polymers , Polymerization , Macromolecules -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10432 , http://hdl.handle.net/10948/d1020142
- Description: This research project focuses on the synthesis of fluorescent polymers with pendant triazole-substituted coumarin side chain units. Copper(I)-catalyzed Huisgen’s 1,3-dipolar cycloaddition of alkynes with azides to form a 1,2,3-triazole ring, a typical example of “click” reaction, has been utilized for the synthesis of a novel vinyl monomer, 2-oxo-3-(4- vinyl-1H-1,2,3-triazol-1-yl)-2H-chromen-7-yl acetate 62. The monomer and its precursors were synthesised and characterized using 1D- and 2D-NMR and FT-IR. Coumarin-containing triazole polymers were synthesised using free radical polymerization. Reversible Addition-Fragmentation Chain Transfer (RAFT)-mediated polymerization was used to synthesise well defined coumarin-containing triazole polymers with moderate PDI values. The polymers were characterised using 1H-NMR and FT-IR. Modelling of the monomer precursor 61 and the monomer 62 at DFT level of approximation provided useful insights into possible conformations adopted by the monomer precursor 61 and the monomer 62. The photophysical properties of the novel monomer and the synthesised polymers were investigated in a polar solvent.
- Full Text:
- Date Issued: 2013
Falcipains as malarial drug targets
- Authors: Kanzi, Aquillah Mumo
- Date: 2013
- Subjects: Malaria Malaria -- Chemotherapy Plasmodium falciparum Antimalarials -- Development Cysteine proteinases Cysteine proteinases -- Inhibitors Papain Drug development Bioinformatics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3897 , http://hdl.handle.net/10962/d1003842
- Description: Malaria is an infectious disease caused by parasites of the Plasmodium genus with mortality rates of more than a million annually, hence a major global public health concern. Plasmodium falciparum (P. falciparum) accounts for over 90% of malaria incidence. Increased resistance to antimalarial drugs by the Plasmodium parasite, coupled with the lack of an effective malaria vaccine necessitates the urgent need for new research avenues to develop novel and more potent antimalarial drugs. This study focused on falcipains, a group of P. falciparum cysteine proteases that belong to the clan CA and papain family C1, that have emerged as potential drug targets due to their involvement in a range of crucial functions in the P. falciparum life cycle. Recently, falcipain-2 has been validated as a drug target but little is known of its Plasmodium orthologs. Currently, there are several falcipain inhibitors that have been identified, most of which are peptide based but none has proceeded to drug development due to associated poor pharmacological profiles and susceptibility to degradation by host cysteine proteases. Non-peptides inhibitors have been shown to be more stable in vivo but limited information exists. In vivo studies on falcipain-2 and falcipain-3 inhibitors have also been complicated by varying outcomes, thus a good understanding of the structural variations of falcipain Plasmodium orthologs at the active site could go a long way to ease in vivo results interpretation and effective inhibitor design. In this study, we use bioinformatics approaches to perform comparative sequence and structural analysis and molecular docking to characterize protein-inhibitor interactions of falcipain homologs at the active site. Known FP-2 and FP-3 small molecule nonpeptide inhibitors were used to identify residue variations and their effect on inhibitor binding. This was done with the aim of screening a collection of selected non-peptide compounds of South African natural origin to identify possible new inhibitor leads. Natural compounds with high binding affinities across all Plasmodium orthologs were identified. These compounds were then used to search the ZINC database for similar compounds which could have better binding affinities across all selected falcipain homologs. Compounds with high binding affinities across all Plasmodium orthologs were found.
- Full Text:
- Date Issued: 2013
- Authors: Kanzi, Aquillah Mumo
- Date: 2013
- Subjects: Malaria Malaria -- Chemotherapy Plasmodium falciparum Antimalarials -- Development Cysteine proteinases Cysteine proteinases -- Inhibitors Papain Drug development Bioinformatics
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3897 , http://hdl.handle.net/10962/d1003842
- Description: Malaria is an infectious disease caused by parasites of the Plasmodium genus with mortality rates of more than a million annually, hence a major global public health concern. Plasmodium falciparum (P. falciparum) accounts for over 90% of malaria incidence. Increased resistance to antimalarial drugs by the Plasmodium parasite, coupled with the lack of an effective malaria vaccine necessitates the urgent need for new research avenues to develop novel and more potent antimalarial drugs. This study focused on falcipains, a group of P. falciparum cysteine proteases that belong to the clan CA and papain family C1, that have emerged as potential drug targets due to their involvement in a range of crucial functions in the P. falciparum life cycle. Recently, falcipain-2 has been validated as a drug target but little is known of its Plasmodium orthologs. Currently, there are several falcipain inhibitors that have been identified, most of which are peptide based but none has proceeded to drug development due to associated poor pharmacological profiles and susceptibility to degradation by host cysteine proteases. Non-peptides inhibitors have been shown to be more stable in vivo but limited information exists. In vivo studies on falcipain-2 and falcipain-3 inhibitors have also been complicated by varying outcomes, thus a good understanding of the structural variations of falcipain Plasmodium orthologs at the active site could go a long way to ease in vivo results interpretation and effective inhibitor design. In this study, we use bioinformatics approaches to perform comparative sequence and structural analysis and molecular docking to characterize protein-inhibitor interactions of falcipain homologs at the active site. Known FP-2 and FP-3 small molecule nonpeptide inhibitors were used to identify residue variations and their effect on inhibitor binding. This was done with the aim of screening a collection of selected non-peptide compounds of South African natural origin to identify possible new inhibitor leads. Natural compounds with high binding affinities across all Plasmodium orthologs were identified. These compounds were then used to search the ZINC database for similar compounds which could have better binding affinities across all selected falcipain homologs. Compounds with high binding affinities across all Plasmodium orthologs were found.
- Full Text:
- Date Issued: 2013
Environmental sustainability leadership in South Africa: an empirical perspective
- Authors: May, Jode Joy
- Date: 2013
- Subjects: Organizational change , Leadership , Business -- Environmental aspects , Strategic planning -- Environmental aspects
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:9320 , http://hdl.handle.net/10948/d1020766
- Description: Striking the balance between managing a successful organisation and paying attention to environmental sustainability requires excellent leadership. There are several benefits associated with being an environmentally sustainable organisation such as improved image (reputation and brand), increased customer loyalty, improved bottom line, attracting skilled experienced staff and improving the relationships with local communities. The purpose of this study was to explore and describe the change leadership qualities needed to drive environmental sustainability in the South African landscape to reduce global warming reduction. The qualitative paradigm was utilised to investigate the change leadership qualities needed to affect create environmental sustainability, with focus on global warming reduction actions in the workplace. A literature review was conducted on environmental sustainability, change leadership, and leadership qualities necessary to effect change. A survey was conducted among 13 participants using an interview schedule in the Gauteng, Western and Eastern Cape provinces of South Africa in both private and public organisations in various business sectors. Data was collected in 2013 over a four–month period by conducting face-to-face, telephonic and email interviews. The returned questionnaires were subjected to constant comparative, content and grounded theory analysis. Biographical profiles of the respondents and participating organisations were presented as case studies. Trustworthiness of the data was ascertained using data triangulation. Data was analysed in terms of the issues of environmental sustainability and change leadership. In-depth analyses were also conducted by means of provincial, business and employment sector comparisons. It was found that environmental sustainability was being addressed by the selected organisations, specifically relating to GHG emissions, energy and water saving actions. Change leaders should implement specific environmental sustainability strategies to assist in the reduction of global warming, create awareness, focus on employee involvement, report on their sustainability results and put and incentives in place to encourage environmental sustainability. In order to effect such changes, change leaders need to set targets to measure their sustainability progress. Green campaigns should be conducted internally to educate employees on the effects of global warming, and externally to inform the public about their commitment to environmental sustainability and to advise the public on courses of actions to assist in the quest to reduce global warming. It would be advisable for organisations to appoint a specific environmental sustainability team to drive these efforts. It was found that in order to bring about such changes, certain qualities were needed by change leaders to enable them to act as a change agents. Associated change leadership styles were also addressed. Change leaders should be knowledgeable in order to effectively communicate the importance of environmental sustainability. They should adopt a blend of leadership styles to drive environmental sustainability depending on the extent of change actions planned. Organisations should identify, appoint and mentor female leaders as they have the nurturing qualities that could successfully drive environmental sustainability actions. Change leaders should also preferably be personally involved in environmental sustainability as their personal values together with their job role at top leadership level could contribute towards successful implementation of environmental sustainability actions in the workplace. The study has provided general guidelines on the environmental sustainability issues necessary to address global warming reduction as well as guidelines on the change leaders qualities necessary to drive environmental sustainability actions in the workplace.
- Full Text:
- Date Issued: 2013
- Authors: May, Jode Joy
- Date: 2013
- Subjects: Organizational change , Leadership , Business -- Environmental aspects , Strategic planning -- Environmental aspects
- Language: English
- Type: Thesis , Masters , MCom
- Identifier: vital:9320 , http://hdl.handle.net/10948/d1020766
- Description: Striking the balance between managing a successful organisation and paying attention to environmental sustainability requires excellent leadership. There are several benefits associated with being an environmentally sustainable organisation such as improved image (reputation and brand), increased customer loyalty, improved bottom line, attracting skilled experienced staff and improving the relationships with local communities. The purpose of this study was to explore and describe the change leadership qualities needed to drive environmental sustainability in the South African landscape to reduce global warming reduction. The qualitative paradigm was utilised to investigate the change leadership qualities needed to affect create environmental sustainability, with focus on global warming reduction actions in the workplace. A literature review was conducted on environmental sustainability, change leadership, and leadership qualities necessary to effect change. A survey was conducted among 13 participants using an interview schedule in the Gauteng, Western and Eastern Cape provinces of South Africa in both private and public organisations in various business sectors. Data was collected in 2013 over a four–month period by conducting face-to-face, telephonic and email interviews. The returned questionnaires were subjected to constant comparative, content and grounded theory analysis. Biographical profiles of the respondents and participating organisations were presented as case studies. Trustworthiness of the data was ascertained using data triangulation. Data was analysed in terms of the issues of environmental sustainability and change leadership. In-depth analyses were also conducted by means of provincial, business and employment sector comparisons. It was found that environmental sustainability was being addressed by the selected organisations, specifically relating to GHG emissions, energy and water saving actions. Change leaders should implement specific environmental sustainability strategies to assist in the reduction of global warming, create awareness, focus on employee involvement, report on their sustainability results and put and incentives in place to encourage environmental sustainability. In order to effect such changes, change leaders need to set targets to measure their sustainability progress. Green campaigns should be conducted internally to educate employees on the effects of global warming, and externally to inform the public about their commitment to environmental sustainability and to advise the public on courses of actions to assist in the quest to reduce global warming. It would be advisable for organisations to appoint a specific environmental sustainability team to drive these efforts. It was found that in order to bring about such changes, certain qualities were needed by change leaders to enable them to act as a change agents. Associated change leadership styles were also addressed. Change leaders should be knowledgeable in order to effectively communicate the importance of environmental sustainability. They should adopt a blend of leadership styles to drive environmental sustainability depending on the extent of change actions planned. Organisations should identify, appoint and mentor female leaders as they have the nurturing qualities that could successfully drive environmental sustainability actions. Change leaders should also preferably be personally involved in environmental sustainability as their personal values together with their job role at top leadership level could contribute towards successful implementation of environmental sustainability actions in the workplace. The study has provided general guidelines on the environmental sustainability issues necessary to address global warming reduction as well as guidelines on the change leaders qualities necessary to drive environmental sustainability actions in the workplace.
- Full Text:
- Date Issued: 2013
Effects of crop rotation and tillage system on the control of ryegrass (lolium multiflorum X perenne) in wheat (triticum aestivum) in the Swartland production area of South Africa's Western Cape Province
- Authors: Nteyi, Sinovuyo Mava
- Date: 2013
- Subjects: Cropping systems , Conservation tillage -- South Africa -- Western Cape , Ryegrasses
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10738 , http://hdl.handle.net/10948/d1020990
- Description: A major challenge facing agriculture today is to sustain the productivity of agricultural systems with the reduction of weed invasion. The Swartland region in the Western Cape (South Africa) is intensively cropped, producing wheat (Triticum aestivum) as the major crop. As a result of the weedy ryegrass invasion the wheat yield is reduced. In addition, ryegrass has developed resistance to grass herbicides (graminicides). This situation has increased the need to use alternative practices for controlling the invasion of ryegrass in wheat fields. In this regard, crop rotation and tillage systems were proposed as techniques to suppress the ryegrass invasion. This could thus maintain a sustainable long-term wheat production system with less application of herbicides, decreased input costs and increased total grain yield. Against this background, the effects of crop rotation and tillage were determined on ryegrass seedling emergence in a field and shade netting experiment, while seed dormancy was determined in the laboratory. The objectives were to compare the wheat production of two crop rotations with mono-cropped wheat and assess the impact on the ryegrass population in no-till and minimum tillage systems. Analyses of variance on data sets of ryegrass seeds from 2009, 2010 and 2011 were used to determine germination and dormancy percentages in laboratory experiments. The performance of laboratory treatments was evaluated on the basis of germination percentage of seeds. In the field and shade netting experiments, analyses of variance for data from 2007, 2011 and 2012 were used to determine crop rotation x tillage system response. Field and shade netting performance were evaluated on the basis of ryegrass population inhibition and stimulation respectively. Ryegrass seeds from 2009 and 2010 showed higher germination percentages (80 per cent and 73 per cent) than 2011 (42 per cent). Primary dormancy prevented high germination of newly harvested seeds as dormancy release increase with age of the seed. Results of field and shade netting experiments showed stimulation of the ryegrass weed population in wheat monoculture under minimum tillage. However, when wheat was rotated with leguminous crops under both tillage systems (minimum-till and no-till) ryegrass was significantly inhibited. It was concluded that the critical period for weed competition is the first six weeks after planting. Results from this study provide a basis for producers of cereals to make good decisions with regards to timing weed control measures. It is essential to use competitive crop sequences which will inhibit weeds. The challenge is getting this practice adopted and implemented by producers as it will promote conservation agriculture within the region. This study promotes long-term sustainable wheat production systems with an efficient weed management programme that is environmentally friendly using less herbicides within the Swartland region.
- Full Text:
- Date Issued: 2013
- Authors: Nteyi, Sinovuyo Mava
- Date: 2013
- Subjects: Cropping systems , Conservation tillage -- South Africa -- Western Cape , Ryegrasses
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10738 , http://hdl.handle.net/10948/d1020990
- Description: A major challenge facing agriculture today is to sustain the productivity of agricultural systems with the reduction of weed invasion. The Swartland region in the Western Cape (South Africa) is intensively cropped, producing wheat (Triticum aestivum) as the major crop. As a result of the weedy ryegrass invasion the wheat yield is reduced. In addition, ryegrass has developed resistance to grass herbicides (graminicides). This situation has increased the need to use alternative practices for controlling the invasion of ryegrass in wheat fields. In this regard, crop rotation and tillage systems were proposed as techniques to suppress the ryegrass invasion. This could thus maintain a sustainable long-term wheat production system with less application of herbicides, decreased input costs and increased total grain yield. Against this background, the effects of crop rotation and tillage were determined on ryegrass seedling emergence in a field and shade netting experiment, while seed dormancy was determined in the laboratory. The objectives were to compare the wheat production of two crop rotations with mono-cropped wheat and assess the impact on the ryegrass population in no-till and minimum tillage systems. Analyses of variance on data sets of ryegrass seeds from 2009, 2010 and 2011 were used to determine germination and dormancy percentages in laboratory experiments. The performance of laboratory treatments was evaluated on the basis of germination percentage of seeds. In the field and shade netting experiments, analyses of variance for data from 2007, 2011 and 2012 were used to determine crop rotation x tillage system response. Field and shade netting performance were evaluated on the basis of ryegrass population inhibition and stimulation respectively. Ryegrass seeds from 2009 and 2010 showed higher germination percentages (80 per cent and 73 per cent) than 2011 (42 per cent). Primary dormancy prevented high germination of newly harvested seeds as dormancy release increase with age of the seed. Results of field and shade netting experiments showed stimulation of the ryegrass weed population in wheat monoculture under minimum tillage. However, when wheat was rotated with leguminous crops under both tillage systems (minimum-till and no-till) ryegrass was significantly inhibited. It was concluded that the critical period for weed competition is the first six weeks after planting. Results from this study provide a basis for producers of cereals to make good decisions with regards to timing weed control measures. It is essential to use competitive crop sequences which will inhibit weeds. The challenge is getting this practice adopted and implemented by producers as it will promote conservation agriculture within the region. This study promotes long-term sustainable wheat production systems with an efficient weed management programme that is environmentally friendly using less herbicides within the Swartland region.
- Full Text:
- Date Issued: 2013
For the people : an appraisal comparison of imagined communities in letters to two South African newspapers
- Authors: Smith, Jade
- Date: 2013
- Subjects: Daily Sun (Johannesburg, South Africa) , Times (Johannesburg, South Africa) , Mass media and social integration -- South Africa , Language and languages -- Usage , Mass media and language -- South Africa , Mass media and culture -- South Africa , Belonging (Social psychology)
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2385 , http://hdl.handle.net/10962/d1016264
- Description: This thesis reports on the bonds that unify imagined communities (Anderson 1983) that are created in 40 letters prominently displayed on the opinions pages of the Daily Sun, a popular tabloid, and The Times, a daily offshoot of the mainstream national Sunday Times. An APPRAISAL analysis of these letters reveals how the imagined communities attempt to align their audiences around distinctive couplings of interpersonal and ideational meaning. Such couplings represent the bonds around which community identities are co-constructed through affiliation and are evidence of the shared feelings that unite the communities of readership. Inferences drawn from this APPRAISAL information allow for a comparison of the natures of the two communities in terms of how they view their agency and group cohesion. Central to the analysis and interpretation of the data is the letters’ evaluative prosody, traced in order to determine the polarity of readers’ stances over four weeks. Asymmetrical prosodies are construed as pointing to the validity of ‘linguistic ventriloquism’, a term whose definition is refined and used as a diagnostic for whether the newspapers use their readers’ letters to promote their own stances on controversial matters. Principal findings show that both communities affiliate around the value of education, and dissatisfaction with the country’s political leaders, however The Times’ readers are more individualistic than the Daily Sun’s community members, who are concerned with the wellbeing of the group. The analysis highlights limitations to the application of the APPRAISAL framework, the value of subjectivity in the analytical process, and adds a new dimension to South African media studies, as it provides linguistic insights into the construction of imagined communities of newspaper readership.
- Full Text:
- Date Issued: 2013
- Authors: Smith, Jade
- Date: 2013
- Subjects: Daily Sun (Johannesburg, South Africa) , Times (Johannesburg, South Africa) , Mass media and social integration -- South Africa , Language and languages -- Usage , Mass media and language -- South Africa , Mass media and culture -- South Africa , Belonging (Social psychology)
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2385 , http://hdl.handle.net/10962/d1016264
- Description: This thesis reports on the bonds that unify imagined communities (Anderson 1983) that are created in 40 letters prominently displayed on the opinions pages of the Daily Sun, a popular tabloid, and The Times, a daily offshoot of the mainstream national Sunday Times. An APPRAISAL analysis of these letters reveals how the imagined communities attempt to align their audiences around distinctive couplings of interpersonal and ideational meaning. Such couplings represent the bonds around which community identities are co-constructed through affiliation and are evidence of the shared feelings that unite the communities of readership. Inferences drawn from this APPRAISAL information allow for a comparison of the natures of the two communities in terms of how they view their agency and group cohesion. Central to the analysis and interpretation of the data is the letters’ evaluative prosody, traced in order to determine the polarity of readers’ stances over four weeks. Asymmetrical prosodies are construed as pointing to the validity of ‘linguistic ventriloquism’, a term whose definition is refined and used as a diagnostic for whether the newspapers use their readers’ letters to promote their own stances on controversial matters. Principal findings show that both communities affiliate around the value of education, and dissatisfaction with the country’s political leaders, however The Times’ readers are more individualistic than the Daily Sun’s community members, who are concerned with the wellbeing of the group. The analysis highlights limitations to the application of the APPRAISAL framework, the value of subjectivity in the analytical process, and adds a new dimension to South African media studies, as it provides linguistic insights into the construction of imagined communities of newspaper readership.
- Full Text:
- Date Issued: 2013
Budget control analysis of logistics companies in Port Elizabeth
- Authors: Phipps, Kaaren Maree
- Date: 2013
- Subjects: Budget -- South Africa -- Port Elizabeth , Budget baselines -- South Africa -- Port Elizabeth , Budget process -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:8946 , http://hdl.handle.net/10948/d1021027
- Description: The treatise analyses the issues around budgets and examines budget expenditure control procedures. The research method selected has been formulated from the research onion process (Saunders, Lewis and Thornhill 2009). This methodology first identifies the research approach, research strategy, timelines and data collection methods. As part of the research process, a quantitative approach has been taken and a survey was carried out in relation to the collection of quantitative data for the purposes of the treatise research. The final analysis of the survey results is reflected in the conclusion of the research findings. Budget expenditure control procedures provide a company with a method of control for managing actual spending against the budget. Most companies have a refined practice of budget preparation, and in the larger companies, these are implemented across all departments and carried out by respective managers. Once the budget is in place, it is the responsibility of the managers to ensure that those having expenditure authorisation adhere to it. If control procedures are well managed, this allows for improved efficiency in operations and can lead to benefits in budget performance. Control procedures that are inefficient and poorly managed will inhibit budget objectives being achieved. The control procedures for budget expenditure can be formulated and applied to optimise budget performance and to control budget variance. Formal budget expenditure control procedures, as part of a company’s budget strategy, can provide managers with an effective business tool that improves current budget spending control procedures. This will then result in the identification of potential efficiency gains and improve budget performance.
- Full Text:
- Date Issued: 2013
- Authors: Phipps, Kaaren Maree
- Date: 2013
- Subjects: Budget -- South Africa -- Port Elizabeth , Budget baselines -- South Africa -- Port Elizabeth , Budget process -- South Africa -- Port Elizabeth
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:8946 , http://hdl.handle.net/10948/d1021027
- Description: The treatise analyses the issues around budgets and examines budget expenditure control procedures. The research method selected has been formulated from the research onion process (Saunders, Lewis and Thornhill 2009). This methodology first identifies the research approach, research strategy, timelines and data collection methods. As part of the research process, a quantitative approach has been taken and a survey was carried out in relation to the collection of quantitative data for the purposes of the treatise research. The final analysis of the survey results is reflected in the conclusion of the research findings. Budget expenditure control procedures provide a company with a method of control for managing actual spending against the budget. Most companies have a refined practice of budget preparation, and in the larger companies, these are implemented across all departments and carried out by respective managers. Once the budget is in place, it is the responsibility of the managers to ensure that those having expenditure authorisation adhere to it. If control procedures are well managed, this allows for improved efficiency in operations and can lead to benefits in budget performance. Control procedures that are inefficient and poorly managed will inhibit budget objectives being achieved. The control procedures for budget expenditure can be formulated and applied to optimise budget performance and to control budget variance. Formal budget expenditure control procedures, as part of a company’s budget strategy, can provide managers with an effective business tool that improves current budget spending control procedures. This will then result in the identification of potential efficiency gains and improve budget performance.
- Full Text:
- Date Issued: 2013
A marine chemical ecology study of the sea hare, Bursatella leachii in South Africa
- Authors: D'Souza, Nicole
- Date: 2013 , 2013-03-22
- Subjects: Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4283 , http://hdl.handle.net/10962/d1002952 , Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Description: The large cosmopolitan sea hare Bursatella leachii is a common resident in Eastern Cape river mouths during summer and late autumn where they congregate in beds of Zostera capensis to breed. In this thesis, the previously known toxic formamide marine secondary metabolite (-)-bursatellin (2.2), which may deter predators of South African specimens of the globally distributed sea hare Bursatella leachii, was isolated and identified (Chapter 2). There have been no previous chemical ecology studies of B. leachii and the latter half of this thesis is devoted to chemical ecology studies of this organism. Interestingly, the isolation of the (-)-diastereomer of 2.2 from specimens of B. leachii collected from the Kariega River mouth (near Kenton-on-Sea) suggests that the South African specimens of this species are similar to specimens collected from Puerto Rico and from the Mediterranean Sea. Two different chromatographic techniques for isolating 2.2 were compared in order to maximize the amount of 2.2 isolated from the Kariega River mouth sea hares. The doubling of selected resonances observed in both the ¹H and ¹³C NMR spectra of the bursatellin isolated in this study suggest one of three possibilities; either firstly, the presence of closely related compound(s), secondly, the presence of diastereomers or thirdly the presence of rotamers. Through NMR kinetic studies, we were able to establish that the presence of rotamers was very unlikely due to no change in the relative ratio (3:1) of the ¹H NMR signals with an increase in temperature. Although the attempted synthesis of the acetate derivative (2.28), as a means of separating a diastereomeric mixture was successful, the chromatographic separation of the proposed acetylated diastereomers was not successful. Preparation of the camphanate ester derivatives (e.g. 2.30) proved to be unsuccessful. Five B. leachii specimens were dissected, their organs separated and individually extracted with methanol. The methanol extracts were individually chromatographed on HP-20 media, and the distribution of bursatellin determined by isolation and NMR. It was evident from this investigation that the distribution of 2.2 within individual B. leachii specimens was found to be highest within the B. leachii ink gland. The lower amounts of 2.2 contained in the digestive system, relative to other organs, was hypothesized to occur because 2.2 is sequestered from the diet of the sea hare and efficiently moved from the gut to various organs around the body where it is stored. The absence of 2.2 from the skin was surprising and may be a result of a smaller mass of skin relative to other organs coupled with the limitations of the chromatographic separation techniques employed. Surprisingly, no bursatellin was found within juvenile sea hares. Chapter three discusses the isolation of ilimaquinone (3.1) and pelorol (3.19) from the sponge Hippospongia metachroma and the structure elucidation of each compound using computer modeling to illustrate the conformation. It was deemed necessary to isolate these well known and abundant bioactive marine natural products from a sponge as standard compounds in the bioassays given the paucity of 2.2 available for this study. Chapter four describes the assays used to test the biological activity of the bursatellin 2.2 compared to the generally bioactive ilimaquinone and the structurally related and commercially available broad spectrum antibiotic chloramphenicol. B. leachii, a shell-less marine mollusc inhabits a variety of intertidal habitats and, therefore, is exposed to several different predators, yet does not appear to have any specific predators. Potential predators of this sea hare in the Kariega Estuary could be fish and amphipods which are found in close proximity to these sea hares. Results of the assays showed that at roughly natural concentrations, (calculated from the isolated chromatographic yield) feeding was deterred by the fish and amphipods, which implied that 2.2 may confer a defensive role within the organism. The relatively high concentration present within the ink gland of B. leachii may support this hypothesis. Surprisingly, given its structural similarity to chloramphenicol, 2.3 did not show any antimicrobial action against five of the six bacterial strains against which it was screened [chloramphenicol inhibited the growth of all the bacterial strains at very low concentrations (0.25 mg/mL)]. Bursatellin was found to be only active against Staphylococus aureus at high concentrations ca. 2 mg/mL when compared to chloramphenicol. Neither bursatellin nor chloramphenicol showed anti-fungal activity. Although this study suggests that the sea hares may use chemical defences in addition to opaline ink to defend themselves, they also live within the seagrass Z. capensis, which possibly provides the sea hare with a cryptic form of physical defence against several predators that are unable to swim freely within the weed beds in the littoral zone of the estuary. , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
- Authors: D'Souza, Nicole
- Date: 2013 , 2013-03-22
- Subjects: Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4283 , http://hdl.handle.net/10962/d1002952 , Sea hares (Mollusks) -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Ecology -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Behavior -- South Africa -- Kenton-on-Sea , Sea hares (Mollusks) -- Defenses -- Behavior -- South Africa -- Kenton-on-Sea
- Description: The large cosmopolitan sea hare Bursatella leachii is a common resident in Eastern Cape river mouths during summer and late autumn where they congregate in beds of Zostera capensis to breed. In this thesis, the previously known toxic formamide marine secondary metabolite (-)-bursatellin (2.2), which may deter predators of South African specimens of the globally distributed sea hare Bursatella leachii, was isolated and identified (Chapter 2). There have been no previous chemical ecology studies of B. leachii and the latter half of this thesis is devoted to chemical ecology studies of this organism. Interestingly, the isolation of the (-)-diastereomer of 2.2 from specimens of B. leachii collected from the Kariega River mouth (near Kenton-on-Sea) suggests that the South African specimens of this species are similar to specimens collected from Puerto Rico and from the Mediterranean Sea. Two different chromatographic techniques for isolating 2.2 were compared in order to maximize the amount of 2.2 isolated from the Kariega River mouth sea hares. The doubling of selected resonances observed in both the ¹H and ¹³C NMR spectra of the bursatellin isolated in this study suggest one of three possibilities; either firstly, the presence of closely related compound(s), secondly, the presence of diastereomers or thirdly the presence of rotamers. Through NMR kinetic studies, we were able to establish that the presence of rotamers was very unlikely due to no change in the relative ratio (3:1) of the ¹H NMR signals with an increase in temperature. Although the attempted synthesis of the acetate derivative (2.28), as a means of separating a diastereomeric mixture was successful, the chromatographic separation of the proposed acetylated diastereomers was not successful. Preparation of the camphanate ester derivatives (e.g. 2.30) proved to be unsuccessful. Five B. leachii specimens were dissected, their organs separated and individually extracted with methanol. The methanol extracts were individually chromatographed on HP-20 media, and the distribution of bursatellin determined by isolation and NMR. It was evident from this investigation that the distribution of 2.2 within individual B. leachii specimens was found to be highest within the B. leachii ink gland. The lower amounts of 2.2 contained in the digestive system, relative to other organs, was hypothesized to occur because 2.2 is sequestered from the diet of the sea hare and efficiently moved from the gut to various organs around the body where it is stored. The absence of 2.2 from the skin was surprising and may be a result of a smaller mass of skin relative to other organs coupled with the limitations of the chromatographic separation techniques employed. Surprisingly, no bursatellin was found within juvenile sea hares. Chapter three discusses the isolation of ilimaquinone (3.1) and pelorol (3.19) from the sponge Hippospongia metachroma and the structure elucidation of each compound using computer modeling to illustrate the conformation. It was deemed necessary to isolate these well known and abundant bioactive marine natural products from a sponge as standard compounds in the bioassays given the paucity of 2.2 available for this study. Chapter four describes the assays used to test the biological activity of the bursatellin 2.2 compared to the generally bioactive ilimaquinone and the structurally related and commercially available broad spectrum antibiotic chloramphenicol. B. leachii, a shell-less marine mollusc inhabits a variety of intertidal habitats and, therefore, is exposed to several different predators, yet does not appear to have any specific predators. Potential predators of this sea hare in the Kariega Estuary could be fish and amphipods which are found in close proximity to these sea hares. Results of the assays showed that at roughly natural concentrations, (calculated from the isolated chromatographic yield) feeding was deterred by the fish and amphipods, which implied that 2.2 may confer a defensive role within the organism. The relatively high concentration present within the ink gland of B. leachii may support this hypothesis. Surprisingly, given its structural similarity to chloramphenicol, 2.3 did not show any antimicrobial action against five of the six bacterial strains against which it was screened [chloramphenicol inhibited the growth of all the bacterial strains at very low concentrations (0.25 mg/mL)]. Bursatellin was found to be only active against Staphylococus aureus at high concentrations ca. 2 mg/mL when compared to chloramphenicol. Neither bursatellin nor chloramphenicol showed anti-fungal activity. Although this study suggests that the sea hares may use chemical defences in addition to opaline ink to defend themselves, they also live within the seagrass Z. capensis, which possibly provides the sea hare with a cryptic form of physical defence against several predators that are unable to swim freely within the weed beds in the littoral zone of the estuary. , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
The contribution of trees to local livelihoods in urban areas
- Authors: Kaoma, Humphrey
- Date: 2013
- Subjects: Trees in cities - -South Africa , Urban ecology (Sociology) -- South Africa , Poverty -- South Africa , Urban forestry -- South Africa , Urban poor -- South Africa , Natural resources -- South Africa , Human-plant relationships -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4734 , http://hdl.handle.net/10962/d1003911 , Trees in cities - -South Africa , Urban ecology (Sociology) -- South Africa , Poverty -- South Africa , Urban forestry -- South Africa , Urban poor -- South Africa , Natural resources -- South Africa , Human-plant relationships -- South Africa
- Description: Trees in natural forests are widely known for their essential contribution to rural livelihoods in developing countries, providing both consumptive and non-consumptive products to rural inhabitants. These benefits are also obtained from trees in urban forests and used by urban households. In the past decades, the role of urban trees to urban livelihoods, municipalities, local and global environment has often been overlooked by researchers and development agencies, and hence are poorly documented, especially in Africa. In South Africa, the increase in urbanisation and urban poverty means many urban residents are expected to be dependent on trees and tree products from homesteads, neighbourhoods and edges of towns. There is however a paucity of literature on the potential of trees in sustaining livelihoods and poverty alleviation in urban areas. This study determined the magnitude and nature of the direct contribution of trees and tree products to local livelihoods in different urban residential areas (informal, Reconstruction and Development Programme (RDP), and township) in three South African towns (Tzaneen, Bela Bela and Zeerust) which cover a rainfall gradient from relatively higher (775 mm p.a.) to low (575 mm p.a.). The results showed that most (90%) households had an interest in planting and managing trees on homesteads, given the high proportion (71%) of residents who had planted trees on their homesteads. The abundance of trees followed the moisture gradient, with Tzaneen having a larger share (46.4%) of trees, followed by Bela Bela (27.5%) and Zeerust (26.1%). Larger plots in the informal residential area accounted for the larger proportion (42.8%) of trees on homesteads, followed by the township (32.9%) and RDP households being the least because they were recently established. Tree density was also higher in the high rainfall town but the pattern did not follow the moisture gradient between Bela Bela and Zeerust due to little rainfall difference. However, tree density across residential areas was similar to the proportion of trees on homesteads in residential areas. The most common tree species were alien, and mainly exotic fruit trees made up two-thirds of the trees encountered. Most households collected various products from urban trees, particularly fuelwood, from edges of towns. This was especially by households with lower cash income. However, fruits were collected from homesteads regardless of the wealth status. Tree products had a significant contribution to the total annual household income, with fuelwood alone contributing up to R5 663 per household per annum, equivalent to two-three month household cash income. Tree products added 20% to total household income, which represents the amount of money households save by collecting tree products for free. Therefore, trees within and around urban areas contribute significantly to livelihoods and reduce poverty in urban areas. There is need therefore to encourage urban residents to plant trees on homesteads and policy makers to come up with policies that promote sustainable harvesting of tree products from areas surrounding urban areas.
- Full Text:
- Date Issued: 2013
- Authors: Kaoma, Humphrey
- Date: 2013
- Subjects: Trees in cities - -South Africa , Urban ecology (Sociology) -- South Africa , Poverty -- South Africa , Urban forestry -- South Africa , Urban poor -- South Africa , Natural resources -- South Africa , Human-plant relationships -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4734 , http://hdl.handle.net/10962/d1003911 , Trees in cities - -South Africa , Urban ecology (Sociology) -- South Africa , Poverty -- South Africa , Urban forestry -- South Africa , Urban poor -- South Africa , Natural resources -- South Africa , Human-plant relationships -- South Africa
- Description: Trees in natural forests are widely known for their essential contribution to rural livelihoods in developing countries, providing both consumptive and non-consumptive products to rural inhabitants. These benefits are also obtained from trees in urban forests and used by urban households. In the past decades, the role of urban trees to urban livelihoods, municipalities, local and global environment has often been overlooked by researchers and development agencies, and hence are poorly documented, especially in Africa. In South Africa, the increase in urbanisation and urban poverty means many urban residents are expected to be dependent on trees and tree products from homesteads, neighbourhoods and edges of towns. There is however a paucity of literature on the potential of trees in sustaining livelihoods and poverty alleviation in urban areas. This study determined the magnitude and nature of the direct contribution of trees and tree products to local livelihoods in different urban residential areas (informal, Reconstruction and Development Programme (RDP), and township) in three South African towns (Tzaneen, Bela Bela and Zeerust) which cover a rainfall gradient from relatively higher (775 mm p.a.) to low (575 mm p.a.). The results showed that most (90%) households had an interest in planting and managing trees on homesteads, given the high proportion (71%) of residents who had planted trees on their homesteads. The abundance of trees followed the moisture gradient, with Tzaneen having a larger share (46.4%) of trees, followed by Bela Bela (27.5%) and Zeerust (26.1%). Larger plots in the informal residential area accounted for the larger proportion (42.8%) of trees on homesteads, followed by the township (32.9%) and RDP households being the least because they were recently established. Tree density was also higher in the high rainfall town but the pattern did not follow the moisture gradient between Bela Bela and Zeerust due to little rainfall difference. However, tree density across residential areas was similar to the proportion of trees on homesteads in residential areas. The most common tree species were alien, and mainly exotic fruit trees made up two-thirds of the trees encountered. Most households collected various products from urban trees, particularly fuelwood, from edges of towns. This was especially by households with lower cash income. However, fruits were collected from homesteads regardless of the wealth status. Tree products had a significant contribution to the total annual household income, with fuelwood alone contributing up to R5 663 per household per annum, equivalent to two-three month household cash income. Tree products added 20% to total household income, which represents the amount of money households save by collecting tree products for free. Therefore, trees within and around urban areas contribute significantly to livelihoods and reduce poverty in urban areas. There is need therefore to encourage urban residents to plant trees on homesteads and policy makers to come up with policies that promote sustainable harvesting of tree products from areas surrounding urban areas.
- Full Text:
- Date Issued: 2013
Novel applications of Morita-Baylis-Hillman methodology in organic synthesis
- Authors: Mciteka, Lulama Patrick
- Date: 2013 , 2013-04-22
- Subjects: Organic compounds -- Synthesis -- Research Asymmetric synthesis Asymmetry (Chemistry) Chemical reactions -- Research Camphor -- Research AZT (Drug) -- Research Chemical inhibitors -- Research Chemistry -- Methodology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4439 , http://hdl.handle.net/10962/d1007598
- Description: The overall approach in the present investigation has been to explore applications of the Morita-Baylis-Hillman (MBH) reaction in asymmetric synthesis and in the continuation of systems with medicinal potential. To this end, a series of varied camphor-derived acrylate esters was prepared to serve as chiral substrates in asymmetric Morita-Baylis- Hillman reactions. Reduction of N-substituted camphor-10-sulfonamides afforded the 3- exo-hydroxy derivatives as the major products. Acylation of the corresponding sodium alkoxides gave the desired 3-exo-acrylate esters, isolation of which was complicated by concomitant formation of hydrochlorinated and diastereomeric competition products. Bulky camphorsulfonamides containing alkyl, dialkyl, aromatic and adamantyl groups were selected as N-substituents with the view of achieving stereoselective outcome in subsequent MBH reactions. The synthesis of novel camphor-derived Morita-Baylis-Hillman adducts using various pyridine-carboxaldehydes proceeded with exceptionally high yields with diastereoselectivities ranging from 7-33 % d.e. Both 1D and 2D NMR and HRMS techniques were employed to confirm the structures and an extensive study of the electropositive fragmentation patterns of a number of camphor-derived chiral acrylate esters was conducted. Attention has also been given to the application of MBH methodology in the construction of heterocyclic ‘cinnamate-like’ AZT conjugates which were designed to serve as dualaction HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. A number of pyridine carboxaldehyde-derived MBH adducts were synthesized using methyl, ethyl and t-butyl acrylates in the presence of 3-hydroxyquinuclidine (3-HQ) as catalyst. The yields for these reactions were excellent. The resulting MBH adducts were acetylated and subjected to aza-Michael addition using propargylamine. The resulting alkylamino compounds were then used in ‘Click reactions’ to form the targeted AZT-conjugates in moderate to excellent yield. In silico docking of computer modelled AZT-conjugates into the HIV-1 integrase and reverse transcriptase enzyme-active sites and potential hydrogen-bonding interaction with active-site amino acid residues were identified. The electrospray MS fragmentations of the AZT and the novel AZT-conjugates were also investigated and common fragmentation pathways were identified.
- Full Text:
- Date Issued: 2013
- Authors: Mciteka, Lulama Patrick
- Date: 2013 , 2013-04-22
- Subjects: Organic compounds -- Synthesis -- Research Asymmetric synthesis Asymmetry (Chemistry) Chemical reactions -- Research Camphor -- Research AZT (Drug) -- Research Chemical inhibitors -- Research Chemistry -- Methodology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4439 , http://hdl.handle.net/10962/d1007598
- Description: The overall approach in the present investigation has been to explore applications of the Morita-Baylis-Hillman (MBH) reaction in asymmetric synthesis and in the continuation of systems with medicinal potential. To this end, a series of varied camphor-derived acrylate esters was prepared to serve as chiral substrates in asymmetric Morita-Baylis- Hillman reactions. Reduction of N-substituted camphor-10-sulfonamides afforded the 3- exo-hydroxy derivatives as the major products. Acylation of the corresponding sodium alkoxides gave the desired 3-exo-acrylate esters, isolation of which was complicated by concomitant formation of hydrochlorinated and diastereomeric competition products. Bulky camphorsulfonamides containing alkyl, dialkyl, aromatic and adamantyl groups were selected as N-substituents with the view of achieving stereoselective outcome in subsequent MBH reactions. The synthesis of novel camphor-derived Morita-Baylis-Hillman adducts using various pyridine-carboxaldehydes proceeded with exceptionally high yields with diastereoselectivities ranging from 7-33 % d.e. Both 1D and 2D NMR and HRMS techniques were employed to confirm the structures and an extensive study of the electropositive fragmentation patterns of a number of camphor-derived chiral acrylate esters was conducted. Attention has also been given to the application of MBH methodology in the construction of heterocyclic ‘cinnamate-like’ AZT conjugates which were designed to serve as dualaction HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. A number of pyridine carboxaldehyde-derived MBH adducts were synthesized using methyl, ethyl and t-butyl acrylates in the presence of 3-hydroxyquinuclidine (3-HQ) as catalyst. The yields for these reactions were excellent. The resulting MBH adducts were acetylated and subjected to aza-Michael addition using propargylamine. The resulting alkylamino compounds were then used in ‘Click reactions’ to form the targeted AZT-conjugates in moderate to excellent yield. In silico docking of computer modelled AZT-conjugates into the HIV-1 integrase and reverse transcriptase enzyme-active sites and potential hydrogen-bonding interaction with active-site amino acid residues were identified. The electrospray MS fragmentations of the AZT and the novel AZT-conjugates were also investigated and common fragmentation pathways were identified.
- Full Text:
- Date Issued: 2013