Computational analysis of known drug resistant mutants of Plasmodium falciparum Dihydrofolate Reductase (PfDHFR) and screening for novel antifolates against the enzyme
- Authors: Tata, Rolland Bantar
- Date: 2022-04-08
- Subjects: Uncatalogued
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/234184 , vital:50170
- Description: Thesis (PhD) -- Faculty of Science, Biochemistry and Microbiology, 2022
- Full Text:
- Date Issued: 2022-04-08
- Authors: Tata, Rolland Bantar
- Date: 2022-04-08
- Subjects: Uncatalogued
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/234184 , vital:50170
- Description: Thesis (PhD) -- Faculty of Science, Biochemistry and Microbiology, 2022
- Full Text:
- Date Issued: 2022-04-08
Singlet oxygen and optical limiting applications of BODIPYs and other molecular dyes
- Authors: May, Aviwe Khanya
- Date: 2022-04-08
- Subjects: Dyes and dyeing Chemistry , Phthalocyanines , Photochemotherapy , Active oxygen , Nonlinear optics , Time-dependent density functional theory , Photochemistry
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294618 , vital:57238 , DOI 10.21504/10962/294620
- Description: A series of structurally diverse novel and previously synthesized BODIPY core dyes are synthesized and characterized in this thesis. These BODIPYs were synthesized using 2-methylpyrrole, 2-ethylpyrrole, 2,4-dimethylpyrrole and 3-ethyl-2,4-dimethylpyrrole as the starting pyrroles. The combination of different pyrroles with the same aldehyde results in BODIPY core dyes that are structural analogues. These core dyes were used as precursors to synthesise halogenated BODIPYs and novel styrylBODIPY dyes, which were successfully characterized using FT-IR and 1H NMR spectroscopy. The halogenated BODIPY core dyes and the styrylBODIPY dyes were also characterized using MALDI-TOF mass spectrometry. The introduction of heavy atoms on the BODIPY core leads to a red shift of the main spectral. In the presence of styryl groups, the main spectral band red shifts to the far red end of the visible region. As expected, the halogenated BODIPY core dyes also had moderate singlet oxygen quantum yields. These halogenated core dyes were found to be suitable as photosensitizers as all the dyes reduced bacterial viability to below 50% during photodynamic antimicrobial chemotherapy (PACT) studies against Staphylococcus aureus. The structure-property relationships studied demonstrate that the presence of protons rather than methyls at the 1,7-positions or iodines at the 2,6-positions results in more favorable PACT activity. This is likely to be related to the greater ability of the meso-aryl to rotate into the plane of the dipyrromethene ligand and suggests that there should be a stronger focus on dyes of this type in future studies in this field. During nonlinear optical (NLO) studies, all the styrylBODIPYs exhibited favorable reverse saturable absorption (RSA) responses. In the absence of methyl groups at the 1,7-positions, the meso-aryl ring lies closer to the π-system of the BODIPY core, enhancing donor (D)–π–acceptor (A) properties and resulting in slightly enhanced optical limiting (OL) parameters. Additionally, there is no evidence that the introduction of heavy atoms at the 2,6-positions significantly enhances OL properties. In a similar manner, alkyl substituents at these positions also do not significantly enhance OL properties; this was studied for the first time using 15 with ethyl groups at the 2,6-positions. The combination of z-scan data and transient spectroscopy for 16 demonstrated that the main mechanism responsible for the NLO properties of nonhalogenated BODIPY dyes is one-photon absorption from the ground state followed by ESA in the singlet manifold. From the NLO studies of 25, OL parameters of 1,3,5-tristyrylBODIPY dyes were found to be similar in magnitude to properties of distyrylBODIPY dyes, but to have less favorable optical properties for OL applications. The OL properties of scandium phthalocyanines were assessed for the first time, since the Sc(III) ion, unusually for a first row transition metal ion, is known to readily form sandwich complexes. The presence of a Sc(III) ion does not significantly enhance the OL properties of phthalocyanines relative to those of rare earth metal ions that also form complexes of this type. Because BODIPYs and phthalocyanines typically absorb significantly in the visible region, transparent PBC polymer thin films of disilane-bridged compounds with minimal absorption in this region were studied and exhibited an excellent RSA response. These compounds may be useful in the design of OL materials that can protect the human eye. The optimized geometries and spectroscopic properties of selected BODIPYs were studied. As expected, the presence of bromine, iodine, ethyl and styryl groups at different positions of the BODIPY core leads to a narrowing of the HOMO–LUMO band gap, which results in a red-shift of the main spectral band. Partial atomic charges have also been calculated for some of the styrylBODIPY dyes studied for application in OL, and electrostatic potential energy maps were also visualized to better assess how the dipole moment of BODIPY dyes can be modulated since this can affect the OL properties. For all the BODIPYs studied, the electronegativity of the atoms present influences charge distribution on the BODIPY structure. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-08
- Authors: May, Aviwe Khanya
- Date: 2022-04-08
- Subjects: Dyes and dyeing Chemistry , Phthalocyanines , Photochemotherapy , Active oxygen , Nonlinear optics , Time-dependent density functional theory , Photochemistry
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/294618 , vital:57238 , DOI 10.21504/10962/294620
- Description: A series of structurally diverse novel and previously synthesized BODIPY core dyes are synthesized and characterized in this thesis. These BODIPYs were synthesized using 2-methylpyrrole, 2-ethylpyrrole, 2,4-dimethylpyrrole and 3-ethyl-2,4-dimethylpyrrole as the starting pyrroles. The combination of different pyrroles with the same aldehyde results in BODIPY core dyes that are structural analogues. These core dyes were used as precursors to synthesise halogenated BODIPYs and novel styrylBODIPY dyes, which were successfully characterized using FT-IR and 1H NMR spectroscopy. The halogenated BODIPY core dyes and the styrylBODIPY dyes were also characterized using MALDI-TOF mass spectrometry. The introduction of heavy atoms on the BODIPY core leads to a red shift of the main spectral. In the presence of styryl groups, the main spectral band red shifts to the far red end of the visible region. As expected, the halogenated BODIPY core dyes also had moderate singlet oxygen quantum yields. These halogenated core dyes were found to be suitable as photosensitizers as all the dyes reduced bacterial viability to below 50% during photodynamic antimicrobial chemotherapy (PACT) studies against Staphylococcus aureus. The structure-property relationships studied demonstrate that the presence of protons rather than methyls at the 1,7-positions or iodines at the 2,6-positions results in more favorable PACT activity. This is likely to be related to the greater ability of the meso-aryl to rotate into the plane of the dipyrromethene ligand and suggests that there should be a stronger focus on dyes of this type in future studies in this field. During nonlinear optical (NLO) studies, all the styrylBODIPYs exhibited favorable reverse saturable absorption (RSA) responses. In the absence of methyl groups at the 1,7-positions, the meso-aryl ring lies closer to the π-system of the BODIPY core, enhancing donor (D)–π–acceptor (A) properties and resulting in slightly enhanced optical limiting (OL) parameters. Additionally, there is no evidence that the introduction of heavy atoms at the 2,6-positions significantly enhances OL properties. In a similar manner, alkyl substituents at these positions also do not significantly enhance OL properties; this was studied for the first time using 15 with ethyl groups at the 2,6-positions. The combination of z-scan data and transient spectroscopy for 16 demonstrated that the main mechanism responsible for the NLO properties of nonhalogenated BODIPY dyes is one-photon absorption from the ground state followed by ESA in the singlet manifold. From the NLO studies of 25, OL parameters of 1,3,5-tristyrylBODIPY dyes were found to be similar in magnitude to properties of distyrylBODIPY dyes, but to have less favorable optical properties for OL applications. The OL properties of scandium phthalocyanines were assessed for the first time, since the Sc(III) ion, unusually for a first row transition metal ion, is known to readily form sandwich complexes. The presence of a Sc(III) ion does not significantly enhance the OL properties of phthalocyanines relative to those of rare earth metal ions that also form complexes of this type. Because BODIPYs and phthalocyanines typically absorb significantly in the visible region, transparent PBC polymer thin films of disilane-bridged compounds with minimal absorption in this region were studied and exhibited an excellent RSA response. These compounds may be useful in the design of OL materials that can protect the human eye. The optimized geometries and spectroscopic properties of selected BODIPYs were studied. As expected, the presence of bromine, iodine, ethyl and styryl groups at different positions of the BODIPY core leads to a narrowing of the HOMO–LUMO band gap, which results in a red-shift of the main spectral band. Partial atomic charges have also been calculated for some of the styrylBODIPY dyes studied for application in OL, and electrostatic potential energy maps were also visualized to better assess how the dipole moment of BODIPY dyes can be modulated since this can affect the OL properties. For all the BODIPYs studied, the electronegativity of the atoms present influences charge distribution on the BODIPY structure. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-08
Visualisation processes in teaching patterns and their generalisation: perceptions and experiences from senior phase mathematics teachers
- Authors: Chatima, Simon
- Date: 2022-04-08
- Subjects: Visual learning South Africa Eastern Cape , Mathematics Study and teaching (Secondary) South Africa Eastern Cape , Mathematics teachers South Africa Eastern Cape Attitudes , Sequences (Mathematics) Study and teaching (Secondary) South Africa Eastern Cape , Constructivism (Education) South Africa Eastern Cape , Mathematics teachers In-service training South Africa Eastern Cape , VIPRO MATHS Project
- Language: English
- Type: Master's thesis , text
- Identifier: http://hdl.handle.net/10962/232936 , vital:50039
- Description: This study investigated how senior phase mathematics teachers used visualisation approaches to teach patterns and their generalisation as a result of an intervention programme. This project is an integral component of the VIPRO MATHS Project and one of a number of post-graduate research projects which has a particular focus on visualisation processes in mathematics education in the Southern African region. This case study of Senior Phase mathematics teachers in the Chris Hani West District (CHW) in the Eastern Cape Province of South Africa used a social constructivist theory. The study is grounded within an interpretive paradigm explanatory qualitative method design. It surveyed thirty-seven Senior Phase mathematics teachers from schools in the CHW district to get an idea of how teachers teach patterns and their generalisation, prior to an intervention process. After the survey, nine teachers were purposively selected to take part in an intervention programme. They were then observed (teaching) and interviewed to get their perceptions about what factors enable and/or constrain the teaching of patterns and their generalisation when visualisation approaches were used. The data from the survey questionnaire responses, the lesson observations and the interviews were analysed qualitatively. The findings from the survey questionnaire responses revealed that teachers in CHW district value the use of visualisation approaches, although they used visuals to teach patterns in a way that lacked depth, skill and rigor prior to the intervention. Challenges such as difficulty in keeping abreast with the prescribed syllabus, the lack of resources, time constraints, and the limited knowledge of algebra learners have for successfully transferring pictorial representations to symbolic presentations, emerged from the survey data. This necessitated the need for an intervention which focused on the use of a variety of visual strategies and tools to teach patterns and their generalisation effectively. Data from lesson observations showed that all observed participant teachers used visuals to generate image- related questions and created platforms for lively classroom discussions. The teachers used the generated questions to build on learners’ prior knowledge and to promote learner understanding of pattern dynamics that stem from pictorial representations. The data from the interviews revealed that teachers’ perceptions had drastically changed after the intervention. This was because they were now equipped and empowered to effectively make use of visual strategies that enabled them to: build on learners’ prior knowledge, to manipulate visuals for the purpose of prompting learning, develop cognitive perception in learners, cultivate learner innovation and originality and enhance problem solving techniques. This study concludes that the use of visuals enhanced conceptual teaching of patterns and their generalisation in the observed participants. This has the potential to provide mathematics education researchers and curriculum developers with a strong basis to include visualisation processes and strategies into the design of policy documents and to initiate further research efforts. The implications for the teachers are that learners need to be taught ways to create and interpret visual representations in order to understand the dynamics of transferring a pictorial pattern to its resultant symbolic representation expressing pattern regularity. It is also hoped that the results of this study will be utilised by mathematics subject advisers and teacher training institutions to improve the teaching of patterns and their generalisation. , Thesis (MEd) -- Faculty of Education, Education, 2022
- Full Text:
- Date Issued: 2022-04-08
- Authors: Chatima, Simon
- Date: 2022-04-08
- Subjects: Visual learning South Africa Eastern Cape , Mathematics Study and teaching (Secondary) South Africa Eastern Cape , Mathematics teachers South Africa Eastern Cape Attitudes , Sequences (Mathematics) Study and teaching (Secondary) South Africa Eastern Cape , Constructivism (Education) South Africa Eastern Cape , Mathematics teachers In-service training South Africa Eastern Cape , VIPRO MATHS Project
- Language: English
- Type: Master's thesis , text
- Identifier: http://hdl.handle.net/10962/232936 , vital:50039
- Description: This study investigated how senior phase mathematics teachers used visualisation approaches to teach patterns and their generalisation as a result of an intervention programme. This project is an integral component of the VIPRO MATHS Project and one of a number of post-graduate research projects which has a particular focus on visualisation processes in mathematics education in the Southern African region. This case study of Senior Phase mathematics teachers in the Chris Hani West District (CHW) in the Eastern Cape Province of South Africa used a social constructivist theory. The study is grounded within an interpretive paradigm explanatory qualitative method design. It surveyed thirty-seven Senior Phase mathematics teachers from schools in the CHW district to get an idea of how teachers teach patterns and their generalisation, prior to an intervention process. After the survey, nine teachers were purposively selected to take part in an intervention programme. They were then observed (teaching) and interviewed to get their perceptions about what factors enable and/or constrain the teaching of patterns and their generalisation when visualisation approaches were used. The data from the survey questionnaire responses, the lesson observations and the interviews were analysed qualitatively. The findings from the survey questionnaire responses revealed that teachers in CHW district value the use of visualisation approaches, although they used visuals to teach patterns in a way that lacked depth, skill and rigor prior to the intervention. Challenges such as difficulty in keeping abreast with the prescribed syllabus, the lack of resources, time constraints, and the limited knowledge of algebra learners have for successfully transferring pictorial representations to symbolic presentations, emerged from the survey data. This necessitated the need for an intervention which focused on the use of a variety of visual strategies and tools to teach patterns and their generalisation effectively. Data from lesson observations showed that all observed participant teachers used visuals to generate image- related questions and created platforms for lively classroom discussions. The teachers used the generated questions to build on learners’ prior knowledge and to promote learner understanding of pattern dynamics that stem from pictorial representations. The data from the interviews revealed that teachers’ perceptions had drastically changed after the intervention. This was because they were now equipped and empowered to effectively make use of visual strategies that enabled them to: build on learners’ prior knowledge, to manipulate visuals for the purpose of prompting learning, develop cognitive perception in learners, cultivate learner innovation and originality and enhance problem solving techniques. This study concludes that the use of visuals enhanced conceptual teaching of patterns and their generalisation in the observed participants. This has the potential to provide mathematics education researchers and curriculum developers with a strong basis to include visualisation processes and strategies into the design of policy documents and to initiate further research efforts. The implications for the teachers are that learners need to be taught ways to create and interpret visual representations in order to understand the dynamics of transferring a pictorial pattern to its resultant symbolic representation expressing pattern regularity. It is also hoped that the results of this study will be utilised by mathematics subject advisers and teacher training institutions to improve the teaching of patterns and their generalisation. , Thesis (MEd) -- Faculty of Education, Education, 2022
- Full Text:
- Date Issued: 2022-04-08
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