Steam activation, characterisation and adsorption studies of activated carbon from maize tassels.
- Olorundare, O F, Msagati, Titus A, Krause, Rui W M, Okonkwo, J O, Mamba, Bhekie B
- Authors: Olorundare, O F , Msagati, Titus A , Krause, Rui W M , Okonkwo, J O , Mamba, Bhekie B
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123847 , vital:35507 , https://doi.org/10.1080/02757540.2013.877001
- Description: In this paper, steam-produced activated carbon (STAC) from maize tassel (MT) was evaluated for its ability to remove basic dye (methylene blue MB) from aqueous solution in a batch adsorption process. The equilibrium experiments were conducted in the range of 50–300 mg/L initial MB concentrations at 30°C, for effect of pH, adsorbent dosage and contact time. The experimental data were analysed by Langmuir, Freundlich and Temkin isotherm models of adsorption. Freundlich adsorption isotherm was found to have highest value of R2(R2=0.97) compared to other models of Langmuir and Temkin having (0.96 and 0.95 respectively). STAC has a high adsorptive capacity for MB dye (200 mg/g) and also showed favourable adsorption for the dye with the separation factor for the dye-activated carbon system. The kinetic data obtained were analysed using pseudo first-order kinetic equation and pseudo second-order kinetic equation. The experimental data fitted well into pseudo second-order kinetic equation, as demonstrated by the high value of R2.
- Full Text:
- Authors: Olorundare, O F , Msagati, Titus A , Krause, Rui W M , Okonkwo, J O , Mamba, Bhekie B
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123847 , vital:35507 , https://doi.org/10.1080/02757540.2013.877001
- Description: In this paper, steam-produced activated carbon (STAC) from maize tassel (MT) was evaluated for its ability to remove basic dye (methylene blue MB) from aqueous solution in a batch adsorption process. The equilibrium experiments were conducted in the range of 50–300 mg/L initial MB concentrations at 30°C, for effect of pH, adsorbent dosage and contact time. The experimental data were analysed by Langmuir, Freundlich and Temkin isotherm models of adsorption. Freundlich adsorption isotherm was found to have highest value of R2(R2=0.97) compared to other models of Langmuir and Temkin having (0.96 and 0.95 respectively). STAC has a high adsorptive capacity for MB dye (200 mg/g) and also showed favourable adsorption for the dye with the separation factor for the dye-activated carbon system. The kinetic data obtained were analysed using pseudo first-order kinetic equation and pseudo second-order kinetic equation. The experimental data fitted well into pseudo second-order kinetic equation, as demonstrated by the high value of R2.
- Full Text:
Strength training and cardiovascular risk post-menses, with particular emphasis on the plasma lipoproteins: a controlled trial
- Authors: Viljoen, Janet Erica
- Date: 2014
- Subjects: Weight training for women -- Physiological aspects , Exercise for women -- Physiological aspects , Middle-aged women -- Health and hygiene , Cardiovascular system -- Diseases , Hypercholesteremia , Blood lipoproteins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5155 , http://hdl.handle.net/10962/d1013578
- Description: Introduction: Cardiovascular disease affects a greater proportion of females than it does males, and is responsible for an estimated 52 percent of female deaths per annum, globally. Due to the loss of oestrogen associated with the menopause, post-menopausal females are at elevated risk for hypercholesterolaemia which is a primary risk factor for cardiovascular disease. It has not yet been conclusively established whether resistance training can be used to ameliorate hypercholesterolaemia. Aim: This randomized controlled trial investigated what effect 12 weeks of progressive resistance training would have on plasma lipoproteins in a sample of post-menopausal females. Methods: Caucasian women (n=30 intervention and n=18 control) between the ages of 55 and 65 years who were not taking hormone replacement therapy were recruited. Participants did not smoke, were sedentary, were not taking any form of cholesterol-lowering medication, had at least one cholesterol abnormality at baseline but were otherwise healthy and able to participate in a strength training programme. Following extensive medical pre-screening, information dissemination and voluntary consent, the sample was divided into two groups. The exercise sample undertook 12 weeks of resistance training on five days of the week. The control group received no intervention. Measurements were obtained at baseline and every four weeks thereafter and included measures of strength, biochemistry (oestradiol, testosterone, full blood lipid profile, glycated haemoglobin and sex hormone binding globulin), anthropometry, morphology and self-reports (dietary intake, energy expenditure and the profile of mood states questionnaire). Results: There was no change to low density lipoprotein cholesterol, high density lipoprotein cholesterol, triglyceride content or total cholesterol as a result of the intervention. Back, chest and leg strength increased significantly (p<0.01) (increases of 51 percent, 35 percent and 43 percent respectively from baseline); waist circumference dropped (p<0.01) by 5 percent overall and diastolic blood pressure decreased significantly (-9 percent, p<0.01) in the exercise cohort but no change was noted in the matched control. Dietary intake, energy expenditure and body mass remained unchanged in both samples. Morphology (sum of skinfolds, estimated body fat content and girth measures) did not change and nor did other biochemical measures (HbA1c and sex hormone binding globulin) or hormone levels (oestradiol and testosterone). Despite the lack of overall change, an important finding was noted in individual results where a clear indication of ‘responders’ and ‘non-responders’ emerged. Conclusion: Overall mean results suggest that 12 weeks resistance training undertaken five days of the week was ineffective in reducing hypercholesterolaemia in this sample. Despite there being no identifying characteristics determined in this sample, evidence of responders and non-responders to the intervention indicates that reliance on mean data may not be sufficient when analysing data from exercise interventions. Therefore, while progressive resistance training had a positive effect on strength, waist circumference and diastolic blood pressure, it did not positively influence the plasma lipoproteins in this cohort of post-menopausal women. , Maiden name: Kelly, Janet Erica
- Full Text:
- Authors: Viljoen, Janet Erica
- Date: 2014
- Subjects: Weight training for women -- Physiological aspects , Exercise for women -- Physiological aspects , Middle-aged women -- Health and hygiene , Cardiovascular system -- Diseases , Hypercholesteremia , Blood lipoproteins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5155 , http://hdl.handle.net/10962/d1013578
- Description: Introduction: Cardiovascular disease affects a greater proportion of females than it does males, and is responsible for an estimated 52 percent of female deaths per annum, globally. Due to the loss of oestrogen associated with the menopause, post-menopausal females are at elevated risk for hypercholesterolaemia which is a primary risk factor for cardiovascular disease. It has not yet been conclusively established whether resistance training can be used to ameliorate hypercholesterolaemia. Aim: This randomized controlled trial investigated what effect 12 weeks of progressive resistance training would have on plasma lipoproteins in a sample of post-menopausal females. Methods: Caucasian women (n=30 intervention and n=18 control) between the ages of 55 and 65 years who were not taking hormone replacement therapy were recruited. Participants did not smoke, were sedentary, were not taking any form of cholesterol-lowering medication, had at least one cholesterol abnormality at baseline but were otherwise healthy and able to participate in a strength training programme. Following extensive medical pre-screening, information dissemination and voluntary consent, the sample was divided into two groups. The exercise sample undertook 12 weeks of resistance training on five days of the week. The control group received no intervention. Measurements were obtained at baseline and every four weeks thereafter and included measures of strength, biochemistry (oestradiol, testosterone, full blood lipid profile, glycated haemoglobin and sex hormone binding globulin), anthropometry, morphology and self-reports (dietary intake, energy expenditure and the profile of mood states questionnaire). Results: There was no change to low density lipoprotein cholesterol, high density lipoprotein cholesterol, triglyceride content or total cholesterol as a result of the intervention. Back, chest and leg strength increased significantly (p<0.01) (increases of 51 percent, 35 percent and 43 percent respectively from baseline); waist circumference dropped (p<0.01) by 5 percent overall and diastolic blood pressure decreased significantly (-9 percent, p<0.01) in the exercise cohort but no change was noted in the matched control. Dietary intake, energy expenditure and body mass remained unchanged in both samples. Morphology (sum of skinfolds, estimated body fat content and girth measures) did not change and nor did other biochemical measures (HbA1c and sex hormone binding globulin) or hormone levels (oestradiol and testosterone). Despite the lack of overall change, an important finding was noted in individual results where a clear indication of ‘responders’ and ‘non-responders’ emerged. Conclusion: Overall mean results suggest that 12 weeks resistance training undertaken five days of the week was ineffective in reducing hypercholesterolaemia in this sample. Despite there being no identifying characteristics determined in this sample, evidence of responders and non-responders to the intervention indicates that reliance on mean data may not be sufficient when analysing data from exercise interventions. Therefore, while progressive resistance training had a positive effect on strength, waist circumference and diastolic blood pressure, it did not positively influence the plasma lipoproteins in this cohort of post-menopausal women. , Maiden name: Kelly, Janet Erica
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Structural bioinformatics analysis of the Hsp40 and Hsp70 molecular chaperones from humans
- Authors: Adeyemi, Samson Adebowale
- Date: 2014
- Subjects: Structural bioinformatics , Molecular chaperones , Heat shock proteins , Protein-protein interactions , Biomolecules
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4171 , http://hdl.handle.net/10962/d1020962
- Description: HSP70 is one of the most important families of molecular chaperone that regulate the folding and transport of client proteins in an ATP dependent manner. The ATPase activity of HSP70 is stimulated through an interaction with its family of HSP40 co-chaperones. There is evidence to suggest that specific partnerships occur between the different HSP40 and HSP70 isoforms. While some of the residues involved in the interaction are known, many of the residues governing the specificity of HSP40-HSP70 partnerships are not precisely defined. It is not currently possible to predict which HSP40 and HSP70 isoforms will interact. We attempted to use bioinformatics to identify residues involved in the specificity of the interaction between the J domain from HSP40 and the ATPase domain from the HSP70 isoforms from humans. A total of 49 HSP40 and 13 HSP70 sequences from humans were retrieved and used for subsequent analyses. The HSP40 J domains and HSP70 ATPase domains were extracted using python scripts and classified according to the subcellular localization of the proteins using localization prediction programs. Motif analysis was carried out using the full length HSP40 proteins and Multiple Sequence Alignment (MSA) was performed to identify conserved residues that may contribute to the J domain – ATPase domain interactions. Phylogenetic inference of the proteins was also performed in order to study their evolutionary relationship. Homology models of the J domains and ATPase domains were generated. The corresponding models were docked using HADDOCK server in order to analyze possible putative interactions between the partner proteins using the Protein Interactions Calculator (PIC). The level of residue conservation was found to be higher in Type I and II HSP40 than in Type III J proteins. While highly conserved residues on helixes II and III could play critical roles in J domain interactions with corresponding HSP70s, conserved residues on helixes I and IV seemed to be significant in keeping the J domain in its right orientation for functional interactions with HSP70s. Our results also showed that helixes II and III formed the interaction interface for binding to HSP70 ATPase domain as well as the linker residues. Finally, data based docking procedures, such as applied in this study, could be an effective method to investigate protein-protein interactions complex of biomolecules.
- Full Text:
- Authors: Adeyemi, Samson Adebowale
- Date: 2014
- Subjects: Structural bioinformatics , Molecular chaperones , Heat shock proteins , Protein-protein interactions , Biomolecules
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4171 , http://hdl.handle.net/10962/d1020962
- Description: HSP70 is one of the most important families of molecular chaperone that regulate the folding and transport of client proteins in an ATP dependent manner. The ATPase activity of HSP70 is stimulated through an interaction with its family of HSP40 co-chaperones. There is evidence to suggest that specific partnerships occur between the different HSP40 and HSP70 isoforms. While some of the residues involved in the interaction are known, many of the residues governing the specificity of HSP40-HSP70 partnerships are not precisely defined. It is not currently possible to predict which HSP40 and HSP70 isoforms will interact. We attempted to use bioinformatics to identify residues involved in the specificity of the interaction between the J domain from HSP40 and the ATPase domain from the HSP70 isoforms from humans. A total of 49 HSP40 and 13 HSP70 sequences from humans were retrieved and used for subsequent analyses. The HSP40 J domains and HSP70 ATPase domains were extracted using python scripts and classified according to the subcellular localization of the proteins using localization prediction programs. Motif analysis was carried out using the full length HSP40 proteins and Multiple Sequence Alignment (MSA) was performed to identify conserved residues that may contribute to the J domain – ATPase domain interactions. Phylogenetic inference of the proteins was also performed in order to study their evolutionary relationship. Homology models of the J domains and ATPase domains were generated. The corresponding models were docked using HADDOCK server in order to analyze possible putative interactions between the partner proteins using the Protein Interactions Calculator (PIC). The level of residue conservation was found to be higher in Type I and II HSP40 than in Type III J proteins. While highly conserved residues on helixes II and III could play critical roles in J domain interactions with corresponding HSP70s, conserved residues on helixes I and IV seemed to be significant in keeping the J domain in its right orientation for functional interactions with HSP70s. Our results also showed that helixes II and III formed the interaction interface for binding to HSP70 ATPase domain as well as the linker residues. Finally, data based docking procedures, such as applied in this study, could be an effective method to investigate protein-protein interactions complex of biomolecules.
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Study South Africa
- International Education Association of South Africa (IEASA), Jooste, Nico
- Authors: International Education Association of South Africa (IEASA) , Jooste, Nico
- Date: 2014
- Subjects: Education, Higher -- South Africa , Education and globalization -- South Africa Student mobility -- Africa International education -- South Africa Education, Higher -- International cooperation , Universities and colleges -- South Africa , Technical Institutes -- South Africa , Vocational guidance -- South Africa
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/64864 , vital:28621 , ISBN 9780620620123
- Description: [Editor's Letter]: This 14th edition of Study South Africa foregrounds the celebration of 20 years of a democratic South Africa. Patrick Fish was commissioned to write a series of articles reflecting the development of South African Higher Education since 1994 for this edition. Reading through this the reader will hopefully experience a sense of the transformation of the South African Higher Education system. Although we all agree in South Africa that we are not done yet, we also recognise that given the South African realities, the change from a race based and fragmented system of higher education to a single but diverse system is well under way. The South African Universities transformed from mostly mono cultural to multicultural institutions that largely reflects the composition of the South African population. The University campuses also demonstrate the institutional appetite to be international. Not only do they jointly house more than 50,000 international students but are also involved in numerous ways in bringing the benefits of being globally connected to the local communities. We are one of the few higher education systems that largely fund our international activities from institutional budgets. This is one of the main reasons that South African Universities practice a style of internationalisation that is relevant to our institutional needs, as well as the local and national needs. Through our internationalisation endeavours we have connected with the rest of Africa in a very special way. Not only do we educate large numbers of students from other African countries but through the South African Higher Education alumni that now live all over the African continent we have built permanent connections that will enhance and develop long standing relationships. IEASA celebrates with all South Africans 20 years of democracy and realise that it is indeed a privilege to be practitioners in transformed ‘knowledge cities’. We are, however, saddened by the incidents of intolerance and destruction in other parts of the world that make the work of higher education institutions impossible, and can only in solidarity with those scholars at risk celebrate with deep appreciation the efforts and determination of those South Africans that made it possible for us to be Universities in a free and democratic society. , 14th Edition
- Full Text:
- Authors: International Education Association of South Africa (IEASA) , Jooste, Nico
- Date: 2014
- Subjects: Education, Higher -- South Africa , Education and globalization -- South Africa Student mobility -- Africa International education -- South Africa Education, Higher -- International cooperation , Universities and colleges -- South Africa , Technical Institutes -- South Africa , Vocational guidance -- South Africa
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/64864 , vital:28621 , ISBN 9780620620123
- Description: [Editor's Letter]: This 14th edition of Study South Africa foregrounds the celebration of 20 years of a democratic South Africa. Patrick Fish was commissioned to write a series of articles reflecting the development of South African Higher Education since 1994 for this edition. Reading through this the reader will hopefully experience a sense of the transformation of the South African Higher Education system. Although we all agree in South Africa that we are not done yet, we also recognise that given the South African realities, the change from a race based and fragmented system of higher education to a single but diverse system is well under way. The South African Universities transformed from mostly mono cultural to multicultural institutions that largely reflects the composition of the South African population. The University campuses also demonstrate the institutional appetite to be international. Not only do they jointly house more than 50,000 international students but are also involved in numerous ways in bringing the benefits of being globally connected to the local communities. We are one of the few higher education systems that largely fund our international activities from institutional budgets. This is one of the main reasons that South African Universities practice a style of internationalisation that is relevant to our institutional needs, as well as the local and national needs. Through our internationalisation endeavours we have connected with the rest of Africa in a very special way. Not only do we educate large numbers of students from other African countries but through the South African Higher Education alumni that now live all over the African continent we have built permanent connections that will enhance and develop long standing relationships. IEASA celebrates with all South Africans 20 years of democracy and realise that it is indeed a privilege to be practitioners in transformed ‘knowledge cities’. We are, however, saddened by the incidents of intolerance and destruction in other parts of the world that make the work of higher education institutions impossible, and can only in solidarity with those scholars at risk celebrate with deep appreciation the efforts and determination of those South Africans that made it possible for us to be Universities in a free and democratic society. , 14th Edition
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Sustainability Assessment of University of Gondar, Gondar, North-west Ethiopia
- Moges, Haimanot G, Kifle, Desalegn W, Lotz-Sisitka, Heila, Woldyohhanes, Solomon M
- Authors: Moges, Haimanot G , Kifle, Desalegn W , Lotz-Sisitka, Heila , Woldyohhanes, Solomon M
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182845 , vital:43885 , xlink:href="https://doi.org/10.1177/0973408214529990"
- Description: The purpose of this article is to provide an overview of the cross-institutional assessment of sustainable development practices in the University of Gondar (UoG). The focus of the assessment was the level of UoG academic departments’ integration of sustainability concerns in teaching, research and community service. Management contributions to sustainable development, student initiatives on sustainability issues and policy statements about sustainable development of UoG were also considered in the assessment. The data collection was based on the Unit-based Sustainability Assessment Tool (USAT); in addition, supplementary information was collected through observations across the four campuses of UoG from January to February 2012.The result of the assessment showed that only a few academic departments have incorporated sustainability concerns in their curricula and teaching approach. The initiation and commitment of academic departments in mainstreaming sustainability concerns in the research and community service delivered were relatively poor. The operation and management of UoG showed inadequate sustainable development practices on waste management, energy utilization and purchasing from environment-friendly companies. In addition, the written policy and statements of UoG did not reflect sustainability in an explicit manner. The university is expected to respond to the key themes defined through sustainability declarations on higher education; there is also a need to establish the relevance of these in relation to the systemic environment. From the study undertaken, we have learnt that sustainability assessment of universities using USAT will be more valuable, if universities have already initiated the embedding of sustainability so that USAT can be used to benchmark the continual improvement.
- Full Text:
- Authors: Moges, Haimanot G , Kifle, Desalegn W , Lotz-Sisitka, Heila , Woldyohhanes, Solomon M
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182845 , vital:43885 , xlink:href="https://doi.org/10.1177/0973408214529990"
- Description: The purpose of this article is to provide an overview of the cross-institutional assessment of sustainable development practices in the University of Gondar (UoG). The focus of the assessment was the level of UoG academic departments’ integration of sustainability concerns in teaching, research and community service. Management contributions to sustainable development, student initiatives on sustainability issues and policy statements about sustainable development of UoG were also considered in the assessment. The data collection was based on the Unit-based Sustainability Assessment Tool (USAT); in addition, supplementary information was collected through observations across the four campuses of UoG from January to February 2012.The result of the assessment showed that only a few academic departments have incorporated sustainability concerns in their curricula and teaching approach. The initiation and commitment of academic departments in mainstreaming sustainability concerns in the research and community service delivered were relatively poor. The operation and management of UoG showed inadequate sustainable development practices on waste management, energy utilization and purchasing from environment-friendly companies. In addition, the written policy and statements of UoG did not reflect sustainability in an explicit manner. The university is expected to respond to the key themes defined through sustainability declarations on higher education; there is also a need to establish the relevance of these in relation to the systemic environment. From the study undertaken, we have learnt that sustainability assessment of universities using USAT will be more valuable, if universities have already initiated the embedding of sustainability so that USAT can be used to benchmark the continual improvement.
- Full Text:
Synthesis and characterization of NaYGdF4 upconversion nanoparticles and an investigation of their effects on the spectroscopic properties of two phthalocyanine dyes
- Authors: Taylor, Jessica Mary
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54621 , vital:26594
- Description: Sphere and star shaped NaYGdF4:Yb/Er(Tm) upconversion nanoparticles were successfully synthesized utilizing a methanol assisted thermal decomposition approach and their chemical, spectroscopic and fluorescence properties were fully characterized. In addition, their influence on the spectroscopic and fluorescence properties of two phthalocyanines (Pcs) (unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) and aluminium octacarboxy phthalocyanine (Cl)AlOCPc) was investigated. Upconversion nanoparticles were found to produce characteristic upconversion fluorescence emissions in the blue, green, red and NIR regions and were also shown to possess paramagnetic properties. Simple mixing with an H2Pc in toluene was found to exert no change on the spectroscopic or fluorescence properties of the Pc while covalent conjugation to a (Cl)AlOCPc resulted in a large Q band blue shift accompanied by a decrease in fluorescence lifetimes in DMSO. The red light excitation mediated singlet oxygen generation of the H2Pc mixed with upconversion nanoparticles was investigated and singlet oxygen fluorescence lifetimes were found to decrease in the presence of the nanoparticles. Upconversion mediated singlet oxygen generation, by way of resonance energy transfer to the Pc, was also attempted using 972 nm excitation; however, no singlet oxygen was detected utilizing singlet oxygen NIR emission detection. Pending further work using alternative singlet oxygen detection methods, this suggests that while upconversion nanoparticles possess excellent fluorescent imaging capabilities, they are relatively inefficient in inducing singlet oxygen production simply when mixed with phthalocyanines. Despite this, by combining phthalocyanines and upconversion nanoparticles, we present a system capable of: multimodal imaging, using both upconversion and phthalocyanines emissions, singlet oxygen generation, via direct excitation of the phthalocyanine with red laser light, and, possibly, magnetic resonance imaging, as a result of doping the upconversion nanoparticles with Gd3+ ions.
- Full Text:
- Authors: Taylor, Jessica Mary
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54621 , vital:26594
- Description: Sphere and star shaped NaYGdF4:Yb/Er(Tm) upconversion nanoparticles were successfully synthesized utilizing a methanol assisted thermal decomposition approach and their chemical, spectroscopic and fluorescence properties were fully characterized. In addition, their influence on the spectroscopic and fluorescence properties of two phthalocyanines (Pcs) (unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) and aluminium octacarboxy phthalocyanine (Cl)AlOCPc) was investigated. Upconversion nanoparticles were found to produce characteristic upconversion fluorescence emissions in the blue, green, red and NIR regions and were also shown to possess paramagnetic properties. Simple mixing with an H2Pc in toluene was found to exert no change on the spectroscopic or fluorescence properties of the Pc while covalent conjugation to a (Cl)AlOCPc resulted in a large Q band blue shift accompanied by a decrease in fluorescence lifetimes in DMSO. The red light excitation mediated singlet oxygen generation of the H2Pc mixed with upconversion nanoparticles was investigated and singlet oxygen fluorescence lifetimes were found to decrease in the presence of the nanoparticles. Upconversion mediated singlet oxygen generation, by way of resonance energy transfer to the Pc, was also attempted using 972 nm excitation; however, no singlet oxygen was detected utilizing singlet oxygen NIR emission detection. Pending further work using alternative singlet oxygen detection methods, this suggests that while upconversion nanoparticles possess excellent fluorescent imaging capabilities, they are relatively inefficient in inducing singlet oxygen production simply when mixed with phthalocyanines. Despite this, by combining phthalocyanines and upconversion nanoparticles, we present a system capable of: multimodal imaging, using both upconversion and phthalocyanines emissions, singlet oxygen generation, via direct excitation of the phthalocyanine with red laser light, and, possibly, magnetic resonance imaging, as a result of doping the upconversion nanoparticles with Gd3+ ions.
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Synthesis and characterization of novel zinc phthalocyanines as potential photosensitizers for photodynamic therapy of cancers
- Moeno, Sharon, Ermilov, E A, Kuzyniak, W, Höpfner, M, Krause, Rui W M
- Authors: Moeno, Sharon , Ermilov, E A , Kuzyniak, W , Höpfner, M , Krause, Rui W M
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123673 , vital:35471 , https://doi.org/10.1039/C3PP50393C
- Description: Two novel zinc phthalocyanines (Pcs): tetramethyl tetrakis-2,(3)-[(4-methyl-2-pyridyloxy)phthalocyaninato] zinc(II) (4) and (the negatively charged form) tetrakis-2,(3)-[(3-carboxylicacid-6-sulfanylpyridine)phthalocyaninato] zinc(II) (5), water soluble by virtue of their ionic substituent groups were synthesized. The spectroscopic properties of both compounds were determined and their photodynamic activities were investigated in a human tumor cell model. In aqueous media the two peripherally substituted water soluble Pcs are highly aggregated. The phototoxic activity of the two novel Pcs (Pc 4 and Pc 5; 0–20 μM) was shown to be time- and dose-dependent in human pancreatic carcinoid BON cells, leading to a reduction of tumor cells of >80% compared to the controls. The effectiveness of the treatment appeared to be attenuated by the aggregation of Pcs under aqueous conditions. Interestingly, even those cells that were not immediately killed by the photoactivated photosensitizer seemed to be affected by the Pc photodynamic activity, as a single PDT induced long-lasting effects on cell survival. Even 4 days after PDT, the number of surviving cells did not re-increase or still dropped, as compared to control cells. The underlying mechanism of this observation has to be deciphered in future investigations.
- Full Text:
- Authors: Moeno, Sharon , Ermilov, E A , Kuzyniak, W , Höpfner, M , Krause, Rui W M
- Date: 2014
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/123673 , vital:35471 , https://doi.org/10.1039/C3PP50393C
- Description: Two novel zinc phthalocyanines (Pcs): tetramethyl tetrakis-2,(3)-[(4-methyl-2-pyridyloxy)phthalocyaninato] zinc(II) (4) and (the negatively charged form) tetrakis-2,(3)-[(3-carboxylicacid-6-sulfanylpyridine)phthalocyaninato] zinc(II) (5), water soluble by virtue of their ionic substituent groups were synthesized. The spectroscopic properties of both compounds were determined and their photodynamic activities were investigated in a human tumor cell model. In aqueous media the two peripherally substituted water soluble Pcs are highly aggregated. The phototoxic activity of the two novel Pcs (Pc 4 and Pc 5; 0–20 μM) was shown to be time- and dose-dependent in human pancreatic carcinoid BON cells, leading to a reduction of tumor cells of >80% compared to the controls. The effectiveness of the treatment appeared to be attenuated by the aggregation of Pcs under aqueous conditions. Interestingly, even those cells that were not immediately killed by the photoactivated photosensitizer seemed to be affected by the Pc photodynamic activity, as a single PDT induced long-lasting effects on cell survival. Even 4 days after PDT, the number of surviving cells did not re-increase or still dropped, as compared to control cells. The underlying mechanism of this observation has to be deciphered in future investigations.
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Synthesis and characterization of quantum dots designed for biomedical use
- Kuzyniak, Weronika, Adegoke, Oluwasesan, Sekhosana, Kutloana E, D'Souza, Sarah, Tshangana, Sesethu Charmaine, Hoffmann, Björn, Ermilov, Eugeny A, Nyokong, Tebello, Höpfner, Michael
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloana E , D'Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A , Nyokong, Tebello , Höpfner, Michael
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241516 , vital:50946 , xlink:href="https://doi.org/10.1016/j.ijpharm.2014.03.037"
- Description: Semiconductor quantum dots (QDs) have become promising nanoparticles for a wide variety of biomedical applications. However, the major drawback of QDs is their potential toxicity. Here, we determined possible cytotoxic effects of a set of QDs by systematic photophysical evaluation in vitro as well as in vivo. QDs were synthesized by the hydrothermal aqueous route with sizes in the range of 2.0–3.5 nm. Cytotoxic effects of QDs were studied in the human pancreatic carcinoid cell line BON. Cadmium telluride QDs with or without zinc sulfide shell and coated with 3-mercaptopropionic acid (MPA) were highly cytotoxic even at nanomolar concentrations. Capping with L-glutathione (GSH) or thioglycolic acid (TGA) reduced the cytotoxicity of cadmium telluride QDs and cadmium selenide QDs. Determination of the toxicity of QDs revealed IC50 values in the micromolar range. In vivo studies showed good tolerability of CdSe QDs with ZnS shell and GSH capping. We could demonstrate that QDs with ZnS shell and GSH capping exhibit low toxicity and good tolerability in cell models and living organisms. These QDs appear to be promising candidates for biomedical applications such as drug delivery for enhanced chemotherapy or targeted delivery of light sensitive substances for photodynamic therapy.
- Full Text:
- Authors: Kuzyniak, Weronika , Adegoke, Oluwasesan , Sekhosana, Kutloana E , D'Souza, Sarah , Tshangana, Sesethu Charmaine , Hoffmann, Björn , Ermilov, Eugeny A , Nyokong, Tebello , Höpfner, Michael
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241516 , vital:50946 , xlink:href="https://doi.org/10.1016/j.ijpharm.2014.03.037"
- Description: Semiconductor quantum dots (QDs) have become promising nanoparticles for a wide variety of biomedical applications. However, the major drawback of QDs is their potential toxicity. Here, we determined possible cytotoxic effects of a set of QDs by systematic photophysical evaluation in vitro as well as in vivo. QDs were synthesized by the hydrothermal aqueous route with sizes in the range of 2.0–3.5 nm. Cytotoxic effects of QDs were studied in the human pancreatic carcinoid cell line BON. Cadmium telluride QDs with or without zinc sulfide shell and coated with 3-mercaptopropionic acid (MPA) were highly cytotoxic even at nanomolar concentrations. Capping with L-glutathione (GSH) or thioglycolic acid (TGA) reduced the cytotoxicity of cadmium telluride QDs and cadmium selenide QDs. Determination of the toxicity of QDs revealed IC50 values in the micromolar range. In vivo studies showed good tolerability of CdSe QDs with ZnS shell and GSH capping. We could demonstrate that QDs with ZnS shell and GSH capping exhibit low toxicity and good tolerability in cell models and living organisms. These QDs appear to be promising candidates for biomedical applications such as drug delivery for enhanced chemotherapy or targeted delivery of light sensitive substances for photodynamic therapy.
- Full Text:
Synthesis and evaluation of novel heterocycles as potential HIV-1 enzyme inhibitors
- Ngnie Tuemgnie, Gaëlle Tatiana
- Authors: Ngnie Tuemgnie, Gaëlle Tatiana
- Date: 2014
- Subjects: Heterocyclic compounds , Enzyme inhibitors , Organic compounds , Green chemistry , Coumarins , HIV (Viruses) Enzymes
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/194293 , vital:45440 , DOI https://doi.org/10.21504/10962/194293
- Description: This project has focussed on the synthesis and the evaluation of organic compounds as potential HIV-1 enzyme inhibitors, by making use of green chemistry (microwave assisted synthesis and click chemistry), palladium catalyzed reactions (Heck and Sonogashira coupling), Baylis Hillman methodology and aldol condensation. These compounds were synthesized in good yields and fully characterised by spectroscopic techniques. Biological assay data revealed that some of the compounds possess high inhibitory activity and their effective inhibitory concentration was as good as those of drugs in clinical use. These potential drug molecules were identified by preliminary investigations carried out by molecular modelling where a trend of their inhibitory activity against different enzymes was anticipated. Benzotriazole-AZT conjugates generated by 1,3-dipolar cycloaddition of anthranilic acid derivatives with AZT showed good inhibitory activity in silico against both HIV-1 protease (PR) and HIV-1 reverse transcriptase (RT) enzymes. Still in line with our dual action strategy, cinnamate ester-AZT conjugates were synthesized in three steps starting from benzaldehyde derivatives with a click reaction at the final step. These compounds also showed some inhibitory activity against HIV-1 RT enzyme (88%). In addition, the cinnamoyl fragment attached to AZT appeared to improve the activity of AZT against HIV-1 RT. Peptide chemistry involving carbonyl diimidazole as a coupling reagent between cinnamic acid derivatives and protected amino acids was used to prepare substituted amino acid derivatives which appeared to be very active against the integrase (IN) enzyme (88%). Commercially available coumarin was iodinated and derivatized through palladium catalyzed Heck and Sonogashira reactions with activated alkenes and a terminal alkyne respectively to afford novel coumarin derivatives in good yields. Optimization studies on the Heck reaction with regards to the phosphine ligand, the palladium catalyst and the solvent were carried out to afford novel formyl substituted cinnamate esters with nonaflyl salicylaldehyde derivatives. , Thesis (PhD) -- Faculty of Science, Chemistry, 2014
- Full Text:
- Authors: Ngnie Tuemgnie, Gaëlle Tatiana
- Date: 2014
- Subjects: Heterocyclic compounds , Enzyme inhibitors , Organic compounds , Green chemistry , Coumarins , HIV (Viruses) Enzymes
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/194293 , vital:45440 , DOI https://doi.org/10.21504/10962/194293
- Description: This project has focussed on the synthesis and the evaluation of organic compounds as potential HIV-1 enzyme inhibitors, by making use of green chemistry (microwave assisted synthesis and click chemistry), palladium catalyzed reactions (Heck and Sonogashira coupling), Baylis Hillman methodology and aldol condensation. These compounds were synthesized in good yields and fully characterised by spectroscopic techniques. Biological assay data revealed that some of the compounds possess high inhibitory activity and their effective inhibitory concentration was as good as those of drugs in clinical use. These potential drug molecules were identified by preliminary investigations carried out by molecular modelling where a trend of their inhibitory activity against different enzymes was anticipated. Benzotriazole-AZT conjugates generated by 1,3-dipolar cycloaddition of anthranilic acid derivatives with AZT showed good inhibitory activity in silico against both HIV-1 protease (PR) and HIV-1 reverse transcriptase (RT) enzymes. Still in line with our dual action strategy, cinnamate ester-AZT conjugates were synthesized in three steps starting from benzaldehyde derivatives with a click reaction at the final step. These compounds also showed some inhibitory activity against HIV-1 RT enzyme (88%). In addition, the cinnamoyl fragment attached to AZT appeared to improve the activity of AZT against HIV-1 RT. Peptide chemistry involving carbonyl diimidazole as a coupling reagent between cinnamic acid derivatives and protected amino acids was used to prepare substituted amino acid derivatives which appeared to be very active against the integrase (IN) enzyme (88%). Commercially available coumarin was iodinated and derivatized through palladium catalyzed Heck and Sonogashira reactions with activated alkenes and a terminal alkyne respectively to afford novel coumarin derivatives in good yields. Optimization studies on the Heck reaction with regards to the phosphine ligand, the palladium catalyst and the solvent were carried out to afford novel formyl substituted cinnamate esters with nonaflyl salicylaldehyde derivatives. , Thesis (PhD) -- Faculty of Science, Chemistry, 2014
- Full Text:
Synthesis and structure-activity relationship studies of 1,4-naphthoquinone derivatives as potential anti-trypanosomal agents
- Authors: Chakaingesu, Chikomborero
- Date: 2014
- Subjects: African trypanosomiasis , Trypanosoma brucei , Naphthoquinone , Protozoan diseases , Drugs -- Structure-activity relationships , Millennium Development Goals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3873 , http://hdl.handle.net/10962/d1020959
- Description: Human African Trypanosomiasis (HAT) is an infectious, vector-borne protozoal disease which is amongst the so-called neglected diseases. In 2000, at a summit of the United Nations, eight Millennium Development Goals (MDGs) were set, to be achieved by 2015. MDG 6 states “to combat HIV/AIDS, malaria & other diseases”. With just under 2 years to go before the end of 2015, HAT is still thriving in developing countries. The drugs currently used for the treatment of HAT are in short supply, have severe side effects and those used to treat late stages of the disease are very difficult to administer. The aforementioned challenges call for research into this neglected disease in order to develop new, safe and easy-to-use medicines. Naphthoquinones are a class of compounds shown to possess anti-parasitic activity, amongst a variety of other biological activities, and therefore this pharmacophore was selected for this study. The purpose of this study was to synthesise derivatives of 2,3-dichloro-1,4- naphthoquinone to be tested for anti-trypanosomal activity and thereafter conduct structureactivity relationship studies. A series of reactions were carried out using thiophenol, phenol and aniline nucleophiles to synthesise thioether (-S-), ether (-O-) and amino (-NH-) derivatives of 2,3-dichloro-1,4-naphthoquinone with various halogen or methyl substituents. Purification of the products was carried out by recrystallisation. Nuclear magnetic resonance (NMR), infra-red (IR) and high pressure liquid chromatography coupled to an electro-spray ionisation mass spectrometer (HPLC-ESI-MS) were the analytical methods used for structural confirmation of the products. There were eighteen 1,4-naphthoquinone derivatives that were successfully synthesised using ethanolic solutions. Unfortunately, attempts to synthesise 1,4-naphthoquinones in reactions involving 2-(trifluoro-methyl)aniline and 2-isopropyl-5-methylphenol were unsuccessful, presumably due to steric hindrance by the bulky ortho-substituents. Although the aims of the synthetic procedures were to obtain both mono- and disubstituted products by nucleophilic displacement of the chlorine atom(s) of 2,3-dichloro-1,4- naphthoquinone, only monosubstituted products were obtained from substitution with aniline and phenol nucleophiles. Thiol nucleophiles, however, selectively yielded disubstituted products only. Synthesised naphthoquinone derivatives were tested against Trypanosoma brucei and calculation of the EC₅₀ values from the obtained dose-response curves was carried out using the four parametric equation. All the 1,4-naphthoquinones showed a degree of potency, except compounds 1b, 3c and 3e, which had little or lack of potency. Structure-activity relationship studies (SARs and QSARs) were carried out to determine which structural features or functional group substituents of the naphthoquinone derivatives contribute or take away from the desired anti-trypanosomal activity. It was found that compounds with the best in vitro anti-trypanosomal potencies in the series of analogous 1,4-naphthoquinone derivatives had EC₅₀ values in the range 2.137 to 2.884 μM. The most potent compound in the series was 2-chloro-3-(4-(trifluoromethyl)phenylamino)-1,4- naphthoquinone 1e; but it was 142-fold less potent than the reference standard of melarsoprol.
- Full Text:
- Authors: Chakaingesu, Chikomborero
- Date: 2014
- Subjects: African trypanosomiasis , Trypanosoma brucei , Naphthoquinone , Protozoan diseases , Drugs -- Structure-activity relationships , Millennium Development Goals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3873 , http://hdl.handle.net/10962/d1020959
- Description: Human African Trypanosomiasis (HAT) is an infectious, vector-borne protozoal disease which is amongst the so-called neglected diseases. In 2000, at a summit of the United Nations, eight Millennium Development Goals (MDGs) were set, to be achieved by 2015. MDG 6 states “to combat HIV/AIDS, malaria & other diseases”. With just under 2 years to go before the end of 2015, HAT is still thriving in developing countries. The drugs currently used for the treatment of HAT are in short supply, have severe side effects and those used to treat late stages of the disease are very difficult to administer. The aforementioned challenges call for research into this neglected disease in order to develop new, safe and easy-to-use medicines. Naphthoquinones are a class of compounds shown to possess anti-parasitic activity, amongst a variety of other biological activities, and therefore this pharmacophore was selected for this study. The purpose of this study was to synthesise derivatives of 2,3-dichloro-1,4- naphthoquinone to be tested for anti-trypanosomal activity and thereafter conduct structureactivity relationship studies. A series of reactions were carried out using thiophenol, phenol and aniline nucleophiles to synthesise thioether (-S-), ether (-O-) and amino (-NH-) derivatives of 2,3-dichloro-1,4-naphthoquinone with various halogen or methyl substituents. Purification of the products was carried out by recrystallisation. Nuclear magnetic resonance (NMR), infra-red (IR) and high pressure liquid chromatography coupled to an electro-spray ionisation mass spectrometer (HPLC-ESI-MS) were the analytical methods used for structural confirmation of the products. There were eighteen 1,4-naphthoquinone derivatives that were successfully synthesised using ethanolic solutions. Unfortunately, attempts to synthesise 1,4-naphthoquinones in reactions involving 2-(trifluoro-methyl)aniline and 2-isopropyl-5-methylphenol were unsuccessful, presumably due to steric hindrance by the bulky ortho-substituents. Although the aims of the synthetic procedures were to obtain both mono- and disubstituted products by nucleophilic displacement of the chlorine atom(s) of 2,3-dichloro-1,4- naphthoquinone, only monosubstituted products were obtained from substitution with aniline and phenol nucleophiles. Thiol nucleophiles, however, selectively yielded disubstituted products only. Synthesised naphthoquinone derivatives were tested against Trypanosoma brucei and calculation of the EC₅₀ values from the obtained dose-response curves was carried out using the four parametric equation. All the 1,4-naphthoquinones showed a degree of potency, except compounds 1b, 3c and 3e, which had little or lack of potency. Structure-activity relationship studies (SARs and QSARs) were carried out to determine which structural features or functional group substituents of the naphthoquinone derivatives contribute or take away from the desired anti-trypanosomal activity. It was found that compounds with the best in vitro anti-trypanosomal potencies in the series of analogous 1,4-naphthoquinone derivatives had EC₅₀ values in the range 2.137 to 2.884 μM. The most potent compound in the series was 2-chloro-3-(4-(trifluoromethyl)phenylamino)-1,4- naphthoquinone 1e; but it was 142-fold less potent than the reference standard of melarsoprol.
- Full Text:
Synthesis of chromium carbene scaffolds for use in medicinal chemistry
- Rafael, Christopher Carlos Ferreira
- Authors: Rafael, Christopher Carlos Ferreira
- Date: 2014
- Subjects: Carbenes (Methylene compounds) , Pharmaceutical chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4456 , http://hdl.handle.net/10962/d1010863 , Carbenes (Methylene compounds) , Pharmaceutical chemistry
- Description: This study involves using methyllithium to synthesize Fischer carbene complexes as precursors for metal templated α,β-unsaturated complexes with potential as acceptors in the Baylis Hillman reaction as well as in Dötz benzannulation. Fischer carbene complexes contain low oxidation state metal centers, are electrophilic in nature and are stabilized by π-donating substituents such as alkoxy and amino groups. The increased electron withdrawing nature of the metal carbonyl moiety was expected to improve the rates of reaction compared to organic carbonyls. Four Fischer carbenes were synthesized via nucleophilic addition of MeLi to chromium and tungsten hexacarbonyl at low temperatures followed by alkylation using either a Meerwein salt (Me₃OBF₄) to give the desired Fischer metal methyl methoxy carbenes or Et₄NBr/alkylhalide to make the corresponding ethoxy and allyloxy carbenes. Characterization was by means of ¹³C NMR, ¹H NMR, and IR. In silico studies were carried out looking at the effect of substituents on the carbene bond. Synthesis of α,β-unsaturated complexes was effected via the aldol condensation route and found to be unfavorable using enolizable aldehydes, although the use of two aryl aldehydes resulted in successful preparation of two α,β-unsaturated complexes. Difficulty in the purification of these complexes hindered their full characterization. Computational studies looked at the effect of substituents on the system as well as variation of the metal from Cr to Mo and W. Synthesis of Baylis Hillman adducts using α,β-unsaturated complexes as acceptors was unsuccessful due to the ease of product oxidization. One potential product was obtained in its crude form although purification was not possible due to oxidation. Computational studies suggested that the oxygen on the ligand negatively impacts the stability of these Fischer carbene derived Baylis Hillman adducts promoting intramolecular oxidation of the metal. The α,β-unsaturated complexes and Baylis Hillman adducts were considered to be candidates to undergo Dötz benzannulation methodology. The use of the α,β-unsaturated complexes in this reaction was generally unsuccessful, both in the microwave and in conventional reflux conditions. Computational studies of these compounds were carried out to facilitate understanding of their stability and configuration.
- Full Text:
- Authors: Rafael, Christopher Carlos Ferreira
- Date: 2014
- Subjects: Carbenes (Methylene compounds) , Pharmaceutical chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4456 , http://hdl.handle.net/10962/d1010863 , Carbenes (Methylene compounds) , Pharmaceutical chemistry
- Description: This study involves using methyllithium to synthesize Fischer carbene complexes as precursors for metal templated α,β-unsaturated complexes with potential as acceptors in the Baylis Hillman reaction as well as in Dötz benzannulation. Fischer carbene complexes contain low oxidation state metal centers, are electrophilic in nature and are stabilized by π-donating substituents such as alkoxy and amino groups. The increased electron withdrawing nature of the metal carbonyl moiety was expected to improve the rates of reaction compared to organic carbonyls. Four Fischer carbenes were synthesized via nucleophilic addition of MeLi to chromium and tungsten hexacarbonyl at low temperatures followed by alkylation using either a Meerwein salt (Me₃OBF₄) to give the desired Fischer metal methyl methoxy carbenes or Et₄NBr/alkylhalide to make the corresponding ethoxy and allyloxy carbenes. Characterization was by means of ¹³C NMR, ¹H NMR, and IR. In silico studies were carried out looking at the effect of substituents on the carbene bond. Synthesis of α,β-unsaturated complexes was effected via the aldol condensation route and found to be unfavorable using enolizable aldehydes, although the use of two aryl aldehydes resulted in successful preparation of two α,β-unsaturated complexes. Difficulty in the purification of these complexes hindered their full characterization. Computational studies looked at the effect of substituents on the system as well as variation of the metal from Cr to Mo and W. Synthesis of Baylis Hillman adducts using α,β-unsaturated complexes as acceptors was unsuccessful due to the ease of product oxidization. One potential product was obtained in its crude form although purification was not possible due to oxidation. Computational studies suggested that the oxygen on the ligand negatively impacts the stability of these Fischer carbene derived Baylis Hillman adducts promoting intramolecular oxidation of the metal. The α,β-unsaturated complexes and Baylis Hillman adducts were considered to be candidates to undergo Dötz benzannulation methodology. The use of the α,β-unsaturated complexes in this reaction was generally unsuccessful, both in the microwave and in conventional reflux conditions. Computational studies of these compounds were carried out to facilitate understanding of their stability and configuration.
- Full Text:
Synthesis of silver nanoparticles and their role against a thiazolekinase enzyme from Plasmodium falciparum
- Yao, Jia
- Authors: Yao, Jia
- Date: 2014
- Subjects: Silver , Nanoparticles , Thiazoles , Plasmodium falciparum , Antimalarials , Malaria -- Chemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4168 , http://hdl.handle.net/10962/d1020894
- Description: Malaria, a mosquito-borne infectious disease, caused by the protozoan Plasmodium genus, is the greatest health challenges worldwide. The plasmodial vitamin B1 biosynthetic enzyme PfThzK diverges significantly, both structurally and functionally from its counterpart in higher eukaryotes, thereby making it particularly attractive as a biomedical target. In the present study, PfThzK was recombinantly produced as 6×His fusion protein in E. coli BL21, purified using nickel affinity chromatography and size exclusion chromatography resulting in 1.03% yield and specific activity 0.28 U/mg. The enzyme was found to be a monomer with a molecular mass of 34 kDa. Characterization of the PfThzK showed an optimum temperature and pH of 37°C and 7.5 respectively, and it is relatively stable (t₁/₂=2.66 h). Ag nanoparticles were synthesized by NaBH₄/tannic acid, and characterized by UV-vis spectroscopy and transmission electron microscopy. The morphologies of these Ag nanoparticles (in terms of size) synthesized by tannic acid appeared to be more controlled with the size of 7.06±2.41 nm, compared with those synthesized by NaBH₄, with the sized of 12.9±4.21 nm. The purified PfThzK was challenged with Ag NPs synthesized by tannic acid, and the results suggested that they competitively inhibited PfThzK (89 %) at low concentrations (5-10 μM) with a Ki = 6.45 μM.
- Full Text:
- Authors: Yao, Jia
- Date: 2014
- Subjects: Silver , Nanoparticles , Thiazoles , Plasmodium falciparum , Antimalarials , Malaria -- Chemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4168 , http://hdl.handle.net/10962/d1020894
- Description: Malaria, a mosquito-borne infectious disease, caused by the protozoan Plasmodium genus, is the greatest health challenges worldwide. The plasmodial vitamin B1 biosynthetic enzyme PfThzK diverges significantly, both structurally and functionally from its counterpart in higher eukaryotes, thereby making it particularly attractive as a biomedical target. In the present study, PfThzK was recombinantly produced as 6×His fusion protein in E. coli BL21, purified using nickel affinity chromatography and size exclusion chromatography resulting in 1.03% yield and specific activity 0.28 U/mg. The enzyme was found to be a monomer with a molecular mass of 34 kDa. Characterization of the PfThzK showed an optimum temperature and pH of 37°C and 7.5 respectively, and it is relatively stable (t₁/₂=2.66 h). Ag nanoparticles were synthesized by NaBH₄/tannic acid, and characterized by UV-vis spectroscopy and transmission electron microscopy. The morphologies of these Ag nanoparticles (in terms of size) synthesized by tannic acid appeared to be more controlled with the size of 7.06±2.41 nm, compared with those synthesized by NaBH₄, with the sized of 12.9±4.21 nm. The purified PfThzK was challenged with Ag NPs synthesized by tannic acid, and the results suggested that they competitively inhibited PfThzK (89 %) at low concentrations (5-10 μM) with a Ki = 6.45 μM.
- Full Text:
Synthesis of ytterbium bisphthalocyanines
- Sekhosana, Kutloana E, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189887 , vital:44943 , xlink:href="https://doi.org/10.1016/j.optmat.2014.05.013"
- Description: Herein we report on the syntheses, photophysico-chemical properties and nonlinear absorption parameters of bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-2-yloxy phthalocyaninato)} ytterbium (III) (3) and bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-4-yloxy phthalocyaninato)} ytterbium (III) (4). The fluorescence and singlet oxygen quantum yields obtained for complexes 3 and 4 are low. The triplet quantum yield obtained for complex 3 is high at ΦT = 0.89 whereas for complex 4 ΦT = 0.48. The third order optical susceptibility values are of the order: 10−11 esu (for complex 3), and 10−13 esu (for complex 4) while the hyperpolarizability values are of the order: 10−28 esu (for complex 3) and 10−31 esu (for complex 4). Complexes 3 and 4 show two-photon absorption coefficients of the order of 10−46 cm4 s/photon and 10−48 cm4 s/photon, and threshold intensities as low as 0.3 J cm−2 and 0.0045 J cm−2, respectively.
- Full Text:
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189887 , vital:44943 , xlink:href="https://doi.org/10.1016/j.optmat.2014.05.013"
- Description: Herein we report on the syntheses, photophysico-chemical properties and nonlinear absorption parameters of bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-2-yloxy phthalocyaninato)} ytterbium (III) (3) and bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-4-yloxy phthalocyaninato)} ytterbium (III) (4). The fluorescence and singlet oxygen quantum yields obtained for complexes 3 and 4 are low. The triplet quantum yield obtained for complex 3 is high at ΦT = 0.89 whereas for complex 4 ΦT = 0.48. The third order optical susceptibility values are of the order: 10−11 esu (for complex 3), and 10−13 esu (for complex 4) while the hyperpolarizability values are of the order: 10−28 esu (for complex 3) and 10−31 esu (for complex 4). Complexes 3 and 4 show two-photon absorption coefficients of the order of 10−46 cm4 s/photon and 10−48 cm4 s/photon, and threshold intensities as low as 0.3 J cm−2 and 0.0045 J cm−2, respectively.
- Full Text:
Synthesis, characterization and photodynamic therapy properties of an octa-4-tert-butylphenoxy-substituted phosphorus (V) triazatetrabenzcorrole
- Shi, Maohu, Tian, Jiangwei, Mkhize, Colin, Kubheka, Gugu, Zhou, Jinfeng, Mack, John, Nyokong, Tebello, Shen, Zhen
- Authors: Shi, Maohu , Tian, Jiangwei , Mkhize, Colin , Kubheka, Gugu , Zhou, Jinfeng , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241494 , vital:50944 , xlink:href="https://doi.org/10.1142/S1088424614500436"
- Description: A novel octa-4-tert-butylphenoxy-substituted phosphorus(V) triazatetrabenzcorrole (PVTBC), has been synthesized and characterized by MALDI-TOF MS and NMR, FT-IR and MCD spectroscopy. The fluorescence emission spectrum was used to determine the fluorescence quantum yield and the quantum yield for singlet oxygen generation was calculated by using 1,3-diphenylisobenzofuran as a scavenger. The photocytoxicity against U87MG cells was measured. The results indicated that PVTBC is potentially useful as an NIR region photosensitizer for photodynamic therapy (PDT).
- Full Text:
- Authors: Shi, Maohu , Tian, Jiangwei , Mkhize, Colin , Kubheka, Gugu , Zhou, Jinfeng , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241494 , vital:50944 , xlink:href="https://doi.org/10.1142/S1088424614500436"
- Description: A novel octa-4-tert-butylphenoxy-substituted phosphorus(V) triazatetrabenzcorrole (PVTBC), has been synthesized and characterized by MALDI-TOF MS and NMR, FT-IR and MCD spectroscopy. The fluorescence emission spectrum was used to determine the fluorescence quantum yield and the quantum yield for singlet oxygen generation was calculated by using 1,3-diphenylisobenzofuran as a scavenger. The photocytoxicity against U87MG cells was measured. The results indicated that PVTBC is potentially useful as an NIR region photosensitizer for photodynamic therapy (PDT).
- Full Text:
Synthesis, photophysicochemical properties and TD-DFT calculations of tetrakis (2-benzoyl-4-chlorophenoxy) phthalocyanines
- Yilmaz, Yusuf, Mack, John, Sener, M Kasim, Sönmez, Mehmet, Nyokong, Tebello
- Authors: Yilmaz, Yusuf , Mack, John , Sener, M Kasim , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241538 , vital:50948 , xlink:href="https://doi.org/10.1142/S1088424614500047"
- Description: The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy.
- Full Text:
- Authors: Yilmaz, Yusuf , Mack, John , Sener, M Kasim , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241538 , vital:50948 , xlink:href="https://doi.org/10.1142/S1088424614500047"
- Description: The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy.
- Full Text:
Synthetic analogues of marine bisindole alkaloids as potent selective inhibitors of MRSA pyruvate kinase
- Veale, Clinton Gareth Lancaster
- Authors: Veale, Clinton Gareth Lancaster
- Date: 2014 , 2014-04-02
- Subjects: Alkaloids , Pyruvate kinase , Staphylococcus aureus , Antibiotics , Sponges -- South Africa , Imidazoles , Biological assay , Antibacterial agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4563 , http://hdl.handle.net/10962/d1020893
- Description: Globally, methicillin resistant Staphylococcus aureus (MRSA) has become increasingly difficult to manage in the clinic and new antibiotics are required. The structure activity relationship (SAR) study presented in this thesis forms part of an international collaborative effort to identify potent and selective inhibitors of an MRSA pyruvate kinase (PK) enzyme target. In earlier work the known marine natural product bromodeoxytopsentin (1.6), isolated from a South African marine sponge Topsentia pachastrelloides, exhibited selective and significant inhibition of MRSA PK (IC₅₀ 60 nM). Accordingly bromodeoxytopsentin provided the initial chemical scaffold around which our SAR study was developed. Following a comprehensive introduction, providing the necessary background to the research described in subsequent Chapters, this thesis has been divided into three major parts. Part one (Chapter 2) documents the synthesis of two natural imidazole containing topsentin analogues 1.40, 1.46, five new synthetic analogues 1.58—1.61, 2.104. In the process we developed a new method for the synthesis of topsentin derivatives via selenium dioxide mediated oxidation of N-Boc protected 3-acetylindoles to yield glyoxal intermediates which were subsequently cyclized and deprotected to yield the desired products. Interestingly we were able to demonstrate a delicate relationship between the relative equivalents of selenium dioxide and water used during the oxidation step, careful manipulation of which was required to prevent the uncontrolled formation of side products. Synthetic compounds 1.40, 1.46, 1.58—1.61 were found to be potent inhibitors of MRSA PK (IC₅₀ 238, 2.1, 23, 1.4, 6.3 and 3.2 nM respectively) with 1000-10000 fold selectivity for MRSA PK over four human orthologs. In the second part of this thesis (Chapter 3) we report the successful synthesis of a cohort of previously unknown thiazole containing bisindole topsentin analogues 1.62—1.68 via a Hantzsch thiazole synthesis. Bioassay results revealed that these compounds were only moderate inhibitors of MRSA PK (IC₅₀ 5.1—20 μM) which suggested that inhibitory activity was significantly reduced upon substitution of the central imidazole ring of topsentin type analogues with a thiazole type ring. In addition in Chapter 3 we describe unsuccessful attempts to regiospecifically synthesize oxazole and imidazole topsentin analogues through a similar Hantzsch method. As a consequence of our efforts in this regard we investigated three key reactions in depth, namely the synthesis of 2.2, 3.38, 3.40, 3.41 via α-bromination of 3-acetylindole and the synthesis of indolyl-3-carbonylnitriles 2.13, 3.45—3.47 and α-oxo-1H-indole-3-thioacetamides 3.48—3.51. The investigation of the latter led to the isolation and elucidation of two anomalous N,N-dimethyl-1H-indole-3-carboxamides 3.52 and 3.53. Finally the third part of this thesis (Chapter 4) deals with in silico assessment of the binding of both the imidazole and thiazole containing bisindole alkaloids to the MRSA PK protein which initially guided our SAR studies. In this chapter we reveal that there appears to be no correlation between in silico binding predictions and in vitro MRSA PK inhibitory bioassay data. Superficially it seems that binding energy as determined by the docking program used for these studies correlated with the size of the indole substituents and did not reflect IC₅₀ MRSA PK inhibitory data. Although this led us to computationally explore possible alternative binding sites no clear alternative has been identified.
- Full Text:
- Authors: Veale, Clinton Gareth Lancaster
- Date: 2014 , 2014-04-02
- Subjects: Alkaloids , Pyruvate kinase , Staphylococcus aureus , Antibiotics , Sponges -- South Africa , Imidazoles , Biological assay , Antibacterial agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4563 , http://hdl.handle.net/10962/d1020893
- Description: Globally, methicillin resistant Staphylococcus aureus (MRSA) has become increasingly difficult to manage in the clinic and new antibiotics are required. The structure activity relationship (SAR) study presented in this thesis forms part of an international collaborative effort to identify potent and selective inhibitors of an MRSA pyruvate kinase (PK) enzyme target. In earlier work the known marine natural product bromodeoxytopsentin (1.6), isolated from a South African marine sponge Topsentia pachastrelloides, exhibited selective and significant inhibition of MRSA PK (IC₅₀ 60 nM). Accordingly bromodeoxytopsentin provided the initial chemical scaffold around which our SAR study was developed. Following a comprehensive introduction, providing the necessary background to the research described in subsequent Chapters, this thesis has been divided into three major parts. Part one (Chapter 2) documents the synthesis of two natural imidazole containing topsentin analogues 1.40, 1.46, five new synthetic analogues 1.58—1.61, 2.104. In the process we developed a new method for the synthesis of topsentin derivatives via selenium dioxide mediated oxidation of N-Boc protected 3-acetylindoles to yield glyoxal intermediates which were subsequently cyclized and deprotected to yield the desired products. Interestingly we were able to demonstrate a delicate relationship between the relative equivalents of selenium dioxide and water used during the oxidation step, careful manipulation of which was required to prevent the uncontrolled formation of side products. Synthetic compounds 1.40, 1.46, 1.58—1.61 were found to be potent inhibitors of MRSA PK (IC₅₀ 238, 2.1, 23, 1.4, 6.3 and 3.2 nM respectively) with 1000-10000 fold selectivity for MRSA PK over four human orthologs. In the second part of this thesis (Chapter 3) we report the successful synthesis of a cohort of previously unknown thiazole containing bisindole topsentin analogues 1.62—1.68 via a Hantzsch thiazole synthesis. Bioassay results revealed that these compounds were only moderate inhibitors of MRSA PK (IC₅₀ 5.1—20 μM) which suggested that inhibitory activity was significantly reduced upon substitution of the central imidazole ring of topsentin type analogues with a thiazole type ring. In addition in Chapter 3 we describe unsuccessful attempts to regiospecifically synthesize oxazole and imidazole topsentin analogues through a similar Hantzsch method. As a consequence of our efforts in this regard we investigated three key reactions in depth, namely the synthesis of 2.2, 3.38, 3.40, 3.41 via α-bromination of 3-acetylindole and the synthesis of indolyl-3-carbonylnitriles 2.13, 3.45—3.47 and α-oxo-1H-indole-3-thioacetamides 3.48—3.51. The investigation of the latter led to the isolation and elucidation of two anomalous N,N-dimethyl-1H-indole-3-carboxamides 3.52 and 3.53. Finally the third part of this thesis (Chapter 4) deals with in silico assessment of the binding of both the imidazole and thiazole containing bisindole alkaloids to the MRSA PK protein which initially guided our SAR studies. In this chapter we reveal that there appears to be no correlation between in silico binding predictions and in vitro MRSA PK inhibitory bioassay data. Superficially it seems that binding energy as determined by the docking program used for these studies correlated with the size of the indole substituents and did not reflect IC₅₀ MRSA PK inhibitory data. Although this led us to computationally explore possible alternative binding sites no clear alternative has been identified.
- Full Text:
Taxonomy and life history of the zebra seabream, Diplodus cervinus (Perciformes: Sparidae), in southern Angola
- Authors: Winkler, Alexander Claus
- Date: 2014
- Subjects: Diplodus -- Classification Fish populations -- Angola Diplodus -- Angola Diplodus -- South Africa Diplodus -- Morphology Fisheries -- Angola Sparidae
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5361 , http://hdl.handle.net/10962/d1012062
- Description: The zebra sea bream, Diplodus cervinus (Sparidae) is an inshore fish comprised of two boreal subspecies from the Gulf of Oman and the Mediterranean / north eastern Atlantic and one austral subspecies from South Africa and southern Angola. The assumption of a single austral subspecies has, however, been questioned due to mounting molecular and morphological evidence suggesting that the cool Benguela current is a vicariant barrier that has separated many synonymous inshore fish species between South Africa and southern Angola. The aims of this thesis are to conduct a comparative morphological analysis of Diplodus cervinus in southern Angola and South Africa in order to classify the southern Angolan population and then to conduct a life history assessment to assess the life history impact of allopatry on this species between the two regions. Results of the morphological findings of the present study (ANOSIM, p < 0.05, Rmeristic = 0.42) and (Rmorphometric = 0.30) along with a concurrent molecular study (FST = 0.4 – 0.6), identified significant divergence between specimens from South Africa (n = 25) and southern Angola (n = 37) and supported stock separation and possibly sub-speciation, depending on the classification criteria utilised. While samples from the two boreal subspecies were not available for the comparative morphological or molecular analysis, comparisons of the colouration patterns between the three subspecies, suggested similarity between the southern Angola and the northern Atlantic / Mediterranean populations. In contrast, the colouration patterns between the southern Angolan and South African specimens differed substantially, further supporting the morphological and molecular results. The distinct morphological divergence between the southern Angolan and South African populations was not reflected within the life history traits of both populations. A combination of methods, including length/age frequency analyses, adult sex ratios and histological analysis was used to determine that this species is a rudimentary hermaphrodite in southern Angola. Peak spawning season was observed between June and July. The overall sex ratio (M: F) was 1:1.52 with females dominating smaller younger size classes and 50% maturity was attained at 210 mm FL and 4.6 years. Females [L(t) = 287.5(1-e⁻°·¹⁸⁽t⁻²·⁸⁴⁾)] grew significantly faster (LRT, p < 0.05) than males [L(t) = 380.19(1-e⁻°·°⁶⁽t⁻⁷·¹²⁾)]. The higher maximum age of the southern Angolan population of D. cervinus (43 years) was older than that of South African individuals sampled in the tsitsikamma national park. The similarities in the life history of the two austral populations are probably a consequence of similar selective pressures in the similar warmtemperate habitats. Evidence to support the above comments was found in the feeding study which showed that the South African and Angolan populations were almost identical, with both populations feeding primarily on amphipods and polychaete worms throughout ontogeny. In contrast, the diet of their boreal conspecifics from the Mediterranean was different, where larger individuals tended to select larger, and more robust, prey items. The life history differences observed between the boreal and austral populations can be attributed to either sampling bias or environmental factors. Sampling biases included the use of different age and growth estimation techniques, while the environmental factors would include differential selective pressures most likely driven by different resource availability and exploitation. The present study provides crucial baseline life history information of a potentially exploitable species off southern Angola as well as information on the life history plasticity of the species. Unfortunately, the current lack of uniformity in the methods used to estimate life history parameters between studies conducted on the boreal and austral populations have complicated our understanding of the evolution of various life history trends in sparid fish. From a management perspective however, the results from the present study can be used to propose management strategies for an emerging trap fishery in southern Angola. Using a balanced exploitation fishery approach (harvesting up to the size-at-100% maturity), the size of the fish traps entrance was calculated based the morphological information from this and other small sparid species that are targeted and was estimated to be 62 mm.
- Full Text:
- Authors: Winkler, Alexander Claus
- Date: 2014
- Subjects: Diplodus -- Classification Fish populations -- Angola Diplodus -- Angola Diplodus -- South Africa Diplodus -- Morphology Fisheries -- Angola Sparidae
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:5361 , http://hdl.handle.net/10962/d1012062
- Description: The zebra sea bream, Diplodus cervinus (Sparidae) is an inshore fish comprised of two boreal subspecies from the Gulf of Oman and the Mediterranean / north eastern Atlantic and one austral subspecies from South Africa and southern Angola. The assumption of a single austral subspecies has, however, been questioned due to mounting molecular and morphological evidence suggesting that the cool Benguela current is a vicariant barrier that has separated many synonymous inshore fish species between South Africa and southern Angola. The aims of this thesis are to conduct a comparative morphological analysis of Diplodus cervinus in southern Angola and South Africa in order to classify the southern Angolan population and then to conduct a life history assessment to assess the life history impact of allopatry on this species between the two regions. Results of the morphological findings of the present study (ANOSIM, p < 0.05, Rmeristic = 0.42) and (Rmorphometric = 0.30) along with a concurrent molecular study (FST = 0.4 – 0.6), identified significant divergence between specimens from South Africa (n = 25) and southern Angola (n = 37) and supported stock separation and possibly sub-speciation, depending on the classification criteria utilised. While samples from the two boreal subspecies were not available for the comparative morphological or molecular analysis, comparisons of the colouration patterns between the three subspecies, suggested similarity between the southern Angola and the northern Atlantic / Mediterranean populations. In contrast, the colouration patterns between the southern Angolan and South African specimens differed substantially, further supporting the morphological and molecular results. The distinct morphological divergence between the southern Angolan and South African populations was not reflected within the life history traits of both populations. A combination of methods, including length/age frequency analyses, adult sex ratios and histological analysis was used to determine that this species is a rudimentary hermaphrodite in southern Angola. Peak spawning season was observed between June and July. The overall sex ratio (M: F) was 1:1.52 with females dominating smaller younger size classes and 50% maturity was attained at 210 mm FL and 4.6 years. Females [L(t) = 287.5(1-e⁻°·¹⁸⁽t⁻²·⁸⁴⁾)] grew significantly faster (LRT, p < 0.05) than males [L(t) = 380.19(1-e⁻°·°⁶⁽t⁻⁷·¹²⁾)]. The higher maximum age of the southern Angolan population of D. cervinus (43 years) was older than that of South African individuals sampled in the tsitsikamma national park. The similarities in the life history of the two austral populations are probably a consequence of similar selective pressures in the similar warmtemperate habitats. Evidence to support the above comments was found in the feeding study which showed that the South African and Angolan populations were almost identical, with both populations feeding primarily on amphipods and polychaete worms throughout ontogeny. In contrast, the diet of their boreal conspecifics from the Mediterranean was different, where larger individuals tended to select larger, and more robust, prey items. The life history differences observed between the boreal and austral populations can be attributed to either sampling bias or environmental factors. Sampling biases included the use of different age and growth estimation techniques, while the environmental factors would include differential selective pressures most likely driven by different resource availability and exploitation. The present study provides crucial baseline life history information of a potentially exploitable species off southern Angola as well as information on the life history plasticity of the species. Unfortunately, the current lack of uniformity in the methods used to estimate life history parameters between studies conducted on the boreal and austral populations have complicated our understanding of the evolution of various life history trends in sparid fish. From a management perspective however, the results from the present study can be used to propose management strategies for an emerging trap fishery in southern Angola. Using a balanced exploitation fishery approach (harvesting up to the size-at-100% maturity), the size of the fish traps entrance was calculated based the morphological information from this and other small sparid species that are targeted and was estimated to be 62 mm.
- Full Text:
Teachers' perceptions of behavioural problems manifested by Grade 11 and 12 learners in three Namibian schools
- Authors: Akawa, Ester Anna Nelago
- Date: 2014
- Subjects: Education, Secondary -- Namibia School children -- Namibia -- Attitudes Learning disabilities -- Social aspects Behavior disorders in children -- Education (Secondary) -- Namibia Children with social disabilities -- Education (Secondary) -- Namibia Emotional problems of children -- Education (Secondary) -- Namibia Teachers -- Job stress -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1962 , http://hdl.handle.net/10962/d1010868
- Description: In Namibia today few learners with behavioural and learning problems are within special schools as most are placed within the mainstream school system. Placing these learners within the mainstream system is part of the policy of Inclusive Education (IE) because it argues that this would benefit these learners and also save resources. IE is concerned with addressing barriers to learning and behavioural problems are regarded as one of these barriers. IE argues for a series of new approaches to the diagnosis and response to learners with behavioural problems. This poses challenges for teachers in mainstream schools. Teachers are at the forefront of this situation as they are usually the first to observe and experience the behavioural problems in the schools and are expected to respond appropriately. They find this situation both challenging and problematic. This research explores a sample of teachers’ perceptions of learners’ behavioural problems. To collect in-depth information, this study followed a qualitative approach with a case study design. The data were collected through semi-structured interviews, supplemented with observation and document analysis. The study consisted of fifteen respondents: three principals, three teacher counsellors and nine teachers from the three selected schools. This study illuminates the types of behaviour that teachers encounter, the impact of these behaviours, the factors seen as contributing to these behaviours, and how teachers and the school system deal with these behaviours. In addition the study applies Bronfenbrenner’s bioecological model (1992) to explain how the behaviours manifested by Grade 11 and 12 learners, and identified as problematic by teachers, are part of an interconnected nested social system. The results from the study indicate the manifestation of behavioural problems to be common occurrences in secondary schools are evident, amongst others, through fighting, bullying, substance abuse, truancy, and disrespect of teachers and authority. The teachers pointed to the prevalence of these problems as well as the serious impact such problems have on these learners, their fellow learners, and on the teachers. The teachers identified a complex array of what they saw as contributing factors located within the school, peer groups, family and home circumstances, the local community, as well within the national education policy, the economy and society. The study points to some specific, as well as broader, lessons and opportunities for action both for those managing the education system at the national level and for schools and teachers.
- Full Text:
- Authors: Akawa, Ester Anna Nelago
- Date: 2014
- Subjects: Education, Secondary -- Namibia School children -- Namibia -- Attitudes Learning disabilities -- Social aspects Behavior disorders in children -- Education (Secondary) -- Namibia Children with social disabilities -- Education (Secondary) -- Namibia Emotional problems of children -- Education (Secondary) -- Namibia Teachers -- Job stress -- Namibia
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1962 , http://hdl.handle.net/10962/d1010868
- Description: In Namibia today few learners with behavioural and learning problems are within special schools as most are placed within the mainstream school system. Placing these learners within the mainstream system is part of the policy of Inclusive Education (IE) because it argues that this would benefit these learners and also save resources. IE is concerned with addressing barriers to learning and behavioural problems are regarded as one of these barriers. IE argues for a series of new approaches to the diagnosis and response to learners with behavioural problems. This poses challenges for teachers in mainstream schools. Teachers are at the forefront of this situation as they are usually the first to observe and experience the behavioural problems in the schools and are expected to respond appropriately. They find this situation both challenging and problematic. This research explores a sample of teachers’ perceptions of learners’ behavioural problems. To collect in-depth information, this study followed a qualitative approach with a case study design. The data were collected through semi-structured interviews, supplemented with observation and document analysis. The study consisted of fifteen respondents: three principals, three teacher counsellors and nine teachers from the three selected schools. This study illuminates the types of behaviour that teachers encounter, the impact of these behaviours, the factors seen as contributing to these behaviours, and how teachers and the school system deal with these behaviours. In addition the study applies Bronfenbrenner’s bioecological model (1992) to explain how the behaviours manifested by Grade 11 and 12 learners, and identified as problematic by teachers, are part of an interconnected nested social system. The results from the study indicate the manifestation of behavioural problems to be common occurrences in secondary schools are evident, amongst others, through fighting, bullying, substance abuse, truancy, and disrespect of teachers and authority. The teachers pointed to the prevalence of these problems as well as the serious impact such problems have on these learners, their fellow learners, and on the teachers. The teachers identified a complex array of what they saw as contributing factors located within the school, peer groups, family and home circumstances, the local community, as well within the national education policy, the economy and society. The study points to some specific, as well as broader, lessons and opportunities for action both for those managing the education system at the national level and for schools and teachers.
- Full Text:
Teachers’ experiences of change : a case study analysis of a school-based intervention in rural Kwazulu-Natal
- Authors: James, Sally Jane
- Date: 2014
- Subjects: David Rattray Foundation , Educational change -- South Africa -- KwaZulu-Natal -- Case studies , Rural schools -- South Africa -- KwaZulu-Natal , Teachers -- Training of -- South Africa -- KwaZulu-Natal , Community and school -- South Africa -- KwaZulu-Natal , KwaZulu-Natal (South Africa) -- Social conditions , KwaZulu-Natal (South Africa) -- Economic conditions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1980 , http://hdl.handle.net/10962/d1013118
- Description: The research presented in this thesis is a case study analysis of the school-based intervention initiated by the David Rattray Foundation [DRF]. David Rattray, a South African historian well known for his contribution to the 1879-1896 Anglo-Zulu War heritage, was murdered in January 2007. In response to his untimely death, the DRF was established by family and friends with the hope of improving education within the Umzinyathi rural municipal district of KwaZulu-Natal. This study consisted of three phases: Phase I (May-December 2011); Phase II (January-December 2012), and Phase III (December 2012-October 2013). During Phase I, the focus was on describing the broader context in which the case is located. It resulted in a narrative account of the emergence of the DRF as a non-governmental organisation [NGO] working towards change within the local rural school community. During Phase II the focus shifted from the broader socio-political and economic context to the human dimension which included teachers, principals, volunteer workers and a district official working in the schools. During Phase II the approach to change adopted by the DRF was critically analysed in relation to models of change described in the literature. Teachers’ experiences of change were also examined. Phase III was a synthesis of the findings from the first two research phases. By drawing on systems and complexity theory perspectives, insights were gained enabling a deep understanding of the DRF’s school-based intervention as a whole. This research is a qualitative study that seeks to understand individual teachers’ experiences and participation in a process of change that reaches beyond the individual and his/her immediate context. The adoption of a realist ontology (Maxwell, 2012) and application of an explanatory heuristic based on the critical realist philosophy of Bhaskar (1979, 1980, 2011) enabled the layered analysis and in-depth interpretation that characterises the study. The findings of the study reveal a complex and ongoing process of change within a rural school context. The results illuminate the efficacy of a collaborative partnership between civil society (the DRF), the local community, under the leadership of a tribal authority, and the local government (KwaZulu-Natal Provincial Department of Education). It also reveals how teachers within this particular context do not have a strong voice in the change process and hence participate only superficially in the school-based intervention. It is probable that the constraining mechanisms revealed through this research are not exclusive to this particular case study, but are common across the South African rural school context. The main contention of this thesis is that these mechanisms need further interrogation in order to enable further change and permit the active participation of teachers in the process.While the study illuminates many of the tensions and problems faced by the schools and the community in which they are located, it also highlights the achievements and selfless attitude of many people working towards change and improvement within the schools. This case study thus provides an example to all South Africans of what can be achieved with commitment and effort.
- Full Text:
- Authors: James, Sally Jane
- Date: 2014
- Subjects: David Rattray Foundation , Educational change -- South Africa -- KwaZulu-Natal -- Case studies , Rural schools -- South Africa -- KwaZulu-Natal , Teachers -- Training of -- South Africa -- KwaZulu-Natal , Community and school -- South Africa -- KwaZulu-Natal , KwaZulu-Natal (South Africa) -- Social conditions , KwaZulu-Natal (South Africa) -- Economic conditions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1980 , http://hdl.handle.net/10962/d1013118
- Description: The research presented in this thesis is a case study analysis of the school-based intervention initiated by the David Rattray Foundation [DRF]. David Rattray, a South African historian well known for his contribution to the 1879-1896 Anglo-Zulu War heritage, was murdered in January 2007. In response to his untimely death, the DRF was established by family and friends with the hope of improving education within the Umzinyathi rural municipal district of KwaZulu-Natal. This study consisted of three phases: Phase I (May-December 2011); Phase II (January-December 2012), and Phase III (December 2012-October 2013). During Phase I, the focus was on describing the broader context in which the case is located. It resulted in a narrative account of the emergence of the DRF as a non-governmental organisation [NGO] working towards change within the local rural school community. During Phase II the focus shifted from the broader socio-political and economic context to the human dimension which included teachers, principals, volunteer workers and a district official working in the schools. During Phase II the approach to change adopted by the DRF was critically analysed in relation to models of change described in the literature. Teachers’ experiences of change were also examined. Phase III was a synthesis of the findings from the first two research phases. By drawing on systems and complexity theory perspectives, insights were gained enabling a deep understanding of the DRF’s school-based intervention as a whole. This research is a qualitative study that seeks to understand individual teachers’ experiences and participation in a process of change that reaches beyond the individual and his/her immediate context. The adoption of a realist ontology (Maxwell, 2012) and application of an explanatory heuristic based on the critical realist philosophy of Bhaskar (1979, 1980, 2011) enabled the layered analysis and in-depth interpretation that characterises the study. The findings of the study reveal a complex and ongoing process of change within a rural school context. The results illuminate the efficacy of a collaborative partnership between civil society (the DRF), the local community, under the leadership of a tribal authority, and the local government (KwaZulu-Natal Provincial Department of Education). It also reveals how teachers within this particular context do not have a strong voice in the change process and hence participate only superficially in the school-based intervention. It is probable that the constraining mechanisms revealed through this research are not exclusive to this particular case study, but are common across the South African rural school context. The main contention of this thesis is that these mechanisms need further interrogation in order to enable further change and permit the active participation of teachers in the process.While the study illuminates many of the tensions and problems faced by the schools and the community in which they are located, it also highlights the achievements and selfless attitude of many people working towards change and improvement within the schools. This case study thus provides an example to all South Africans of what can be achieved with commitment and effort.
- Full Text:
Teachers’ understanding and implementation of inclusive education in an Eastern Cape primary school
- Authors: Mcconnachie, Karola
- Date: 2014
- Subjects: Inclusive education -- South Africa , Special education -- South Africa , Education (Primary) -- Government policy -- South Africa , Alcoholism -- Social aspects -- South Africa
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1984 , http://hdl.handle.net/10962/d1013150
- Description: Since 2001 the South African Department of Basic Education has been working towards implementing Inclusive Education over a twenty year period. This is in accordance with international trends in education. This study set out to investigate the implementation of Inclusive Education in a South African context by conducting a case study at an Eastern Cape no‐fee‐paying primary school. It looked at how the government policy, as set out in Education White Paper 6 (EWP6) (DoE, 2001), is understood and being implemented by teachers at the Welcome Primary school. The study further investigated the introduction of the National Strategy on Screening, Identification, Assessment and Support (SIAS strategy) (DoE, 2008a) to gain insight into how teachers identify and assess barriers to learning in an ordinary primary school. In addition it looked at emerging factors that could impact on the implementation of this policy. With 16 years teaching experience in ordinary and private schools and 19 years experience in a special needs school as a teacher, head of department and then principal, I have personal experience of the crisis in the Eastern Cape Department of Basic Education. This awareness provided the impetus and interest in researching Inclusive Education policy implementation. It is my view that only when we begin to grapple with the problems right at the source of the education crisis within the majority of the no‐fee‐paying schools that informed decisions about policy and policy implementation can be made. As I am able to understand and converse in isiXhosa, I was able to observe and experience the implementation of EWP6 and the SIAS strategy in a school that is an isiXhosa‐medium ordinary primary school and similar to the majority of ordinary public schools in the district. A qualitative research approach based within an interpretive paradigm using the case study method was used for this study. Semi‐structured interviews, detailed field notes as well as documents generated by meetings and education conferences helped me to investigate and refine my research goals. The research found that the implementation of EWP6 and the SIAS strategy posed a major challenge for the Department of Basic Education, and highlighted the significant gap between ordinary primary schools and special needs schools. However, the fact that there is a partial engagement with the process of providing inclusive education, does present some measure of hope for a better future for those learners that have experienced the injustice of exclusion from education and society. The Eastern Cape Department of Basic Education will have to ‘catch up’ to other provinces in its delivery of every child’s constitutional right to education in an inclusive school environment. Factors emerged from the study that showed that the assessment of learners’ barriers to learning with the resultant support needs was a relatively new concept, as teachers tended to rely on traditional classroom tests and simple informal classroom assessments to assess the learners. Teachers expressed a good verbal knowledge of learners with support needs but found it very challenging to put this verbal knowledge into a written document. In addition there was inadequate support from the District Based Support Team to implement the SIAS strategy. This study showed that the medical model of assessment was still being adhered to in the research district with little evidence of a move to a social model of assessment in terms of the SIAS strategy. In addition, factors emerged indicating the serious impact that alcohol abuse has on children and the society in which they live. The evidence of increasing numbers of children with Fetal Alcohol Spectrum Disorder (FASD) in a single educational district is a matter of grave concern from an educational and financial perspective. It is my contention that this is a matter of national urgency and that the Department of Basic Education must confront the escalating problem of alcohol abuse and the resultant challenges of a large number of learners with serious barriers to learning that need to be included in the education system.
- Full Text:
- Authors: Mcconnachie, Karola
- Date: 2014
- Subjects: Inclusive education -- South Africa , Special education -- South Africa , Education (Primary) -- Government policy -- South Africa , Alcoholism -- Social aspects -- South Africa
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1984 , http://hdl.handle.net/10962/d1013150
- Description: Since 2001 the South African Department of Basic Education has been working towards implementing Inclusive Education over a twenty year period. This is in accordance with international trends in education. This study set out to investigate the implementation of Inclusive Education in a South African context by conducting a case study at an Eastern Cape no‐fee‐paying primary school. It looked at how the government policy, as set out in Education White Paper 6 (EWP6) (DoE, 2001), is understood and being implemented by teachers at the Welcome Primary school. The study further investigated the introduction of the National Strategy on Screening, Identification, Assessment and Support (SIAS strategy) (DoE, 2008a) to gain insight into how teachers identify and assess barriers to learning in an ordinary primary school. In addition it looked at emerging factors that could impact on the implementation of this policy. With 16 years teaching experience in ordinary and private schools and 19 years experience in a special needs school as a teacher, head of department and then principal, I have personal experience of the crisis in the Eastern Cape Department of Basic Education. This awareness provided the impetus and interest in researching Inclusive Education policy implementation. It is my view that only when we begin to grapple with the problems right at the source of the education crisis within the majority of the no‐fee‐paying schools that informed decisions about policy and policy implementation can be made. As I am able to understand and converse in isiXhosa, I was able to observe and experience the implementation of EWP6 and the SIAS strategy in a school that is an isiXhosa‐medium ordinary primary school and similar to the majority of ordinary public schools in the district. A qualitative research approach based within an interpretive paradigm using the case study method was used for this study. Semi‐structured interviews, detailed field notes as well as documents generated by meetings and education conferences helped me to investigate and refine my research goals. The research found that the implementation of EWP6 and the SIAS strategy posed a major challenge for the Department of Basic Education, and highlighted the significant gap between ordinary primary schools and special needs schools. However, the fact that there is a partial engagement with the process of providing inclusive education, does present some measure of hope for a better future for those learners that have experienced the injustice of exclusion from education and society. The Eastern Cape Department of Basic Education will have to ‘catch up’ to other provinces in its delivery of every child’s constitutional right to education in an inclusive school environment. Factors emerged from the study that showed that the assessment of learners’ barriers to learning with the resultant support needs was a relatively new concept, as teachers tended to rely on traditional classroom tests and simple informal classroom assessments to assess the learners. Teachers expressed a good verbal knowledge of learners with support needs but found it very challenging to put this verbal knowledge into a written document. In addition there was inadequate support from the District Based Support Team to implement the SIAS strategy. This study showed that the medical model of assessment was still being adhered to in the research district with little evidence of a move to a social model of assessment in terms of the SIAS strategy. In addition, factors emerged indicating the serious impact that alcohol abuse has on children and the society in which they live. The evidence of increasing numbers of children with Fetal Alcohol Spectrum Disorder (FASD) in a single educational district is a matter of grave concern from an educational and financial perspective. It is my contention that this is a matter of national urgency and that the Department of Basic Education must confront the escalating problem of alcohol abuse and the resultant challenges of a large number of learners with serious barriers to learning that need to be included in the education system.
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