Novel, soluble, FluXoro functional substituted zinc phthalocyanines; synthesis, characterization and photophysicochemical properties
- Erdoğmuş, Ali, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261258 , vital:53378 , xlink:href="https://doi.org/10.1016/j.dyepig.2010.01.001"
- Description: Three novel phthalonitriles and the respective, peripheral tetrakis zinc phthalocyanines were synthesized and characterized using elemental analysis, IR, 1H NMR, mass spectra and electronic spectroscopy. The phthalocyanines displayed good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene. The presence of a long chain fluorine substitituent was found to result in reduced aggregation. The singlet oxygen, photodegradation, fluorescence quantum yield, triplet quantum yield and triplet life time of the complexes in toluene were determined. The effect of fluoro-functional groups on the photophysical and photochemical parameters of the zinc(II) phthalocyanines are also reported. Fluorescence quantum yields for the complexes ranged from 0.021 to 0.041.
- Full Text:
- Date Issued: 2010
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261258 , vital:53378 , xlink:href="https://doi.org/10.1016/j.dyepig.2010.01.001"
- Description: Three novel phthalonitriles and the respective, peripheral tetrakis zinc phthalocyanines were synthesized and characterized using elemental analysis, IR, 1H NMR, mass spectra and electronic spectroscopy. The phthalocyanines displayed good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene. The presence of a long chain fluorine substitituent was found to result in reduced aggregation. The singlet oxygen, photodegradation, fluorescence quantum yield, triplet quantum yield and triplet life time of the complexes in toluene were determined. The effect of fluoro-functional groups on the photophysical and photochemical parameters of the zinc(II) phthalocyanines are also reported. Fluorescence quantum yields for the complexes ranged from 0.021 to 0.041.
- Full Text:
- Date Issued: 2010
Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands
- Yumata, Nonzaliseko Christine
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
- Authors: Yumata, Nonzaliseko Christine
- Date: 2010
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10373 , http://hdl.handle.net/10948/1085 , Rhenium , Ligands
- Description: The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.
- Full Text:
- Date Issued: 2010
Studies towards the development of novel HIV-1 integrase inhibitors
- Authors: Lee, Yi-Chen
- Date: 2010
- Subjects: HIV infections -- Treatment , HIV (Viruses) , AIDS (Disease) -- Treatment , Nuclear magnetic resonance , Heterocyclic compounds -- Derivatives , Enzyme inhibitors , Chemical inhibitors , Quinoline
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4357 , http://hdl.handle.net/10962/d1005022 , HIV infections -- Treatment , HIV (Viruses) , AIDS (Disease) -- Treatment , Nuclear magnetic resonance , Heterocyclic compounds -- Derivatives , Enzyme inhibitors , Chemical inhibitors , Quinoline
- Description: The project has focused on the preparation of several series of compounds designed as potential HIV-1 integrase inhibitors. Various 2-nitrobenzaldehydes have been reacted with two activated alkenes, methyl vinyl ketone (MVK) and methyl acrylate, under Baylis-Hillman conditions to afford α-methylene-β-hydroxylalkyl derivatives in moderate to excellent yields. The reactions were conducted using the tertiary amine catalysts, 1,4-diazabicyclo[2.2.2]octane(DABCO) or 3-hydroxyquinuclidine (3-HQ) with chloroform as solvent, and yields were optimised by varying the catalyst, reagent concentrations and the reaction time. Reductive cyclization of the Baylis-Hillman adducts via catalytic hydrogenation, using 10% palladiumon-carbon catalyst in ethanol, afforded quinoline and quinoline N-oxide derivatives. In some cases “acyclic” reduction products were also isolated. Reaction of the Baylis-Hillman MVK adducts with HCl, has resulted in effective nucleophilic (SN’) displacement of the hydroxyl group to afford allylic chloride derivatives. Direct substitution of these chloro derivatives by secondary or primary amines, followed by catalytic hydrogenation gave quinoline derivatives containing a 3-aminomethyl substituent. The Baylis-Hillman ester adducts obtained from reaction with methyl acrylate were treated directly with various amines to give diastereomeric conjugate addition products. Reactions with piperazine gave N,N’-disubstituted piperazine products. The piperidine derivatives have been dehydrated to give cinnamate esters in moderate yields. The products, which have all been satisfactorily characterised by elemental (HRMS) and spectroscopic (1- and 2-D NMR) analysis, constitute a “library” of compounds for in silico and in vitro studies as potential HIV integrase inhibitors.
- Full Text:
- Date Issued: 2010
- Authors: Lee, Yi-Chen
- Date: 2010
- Subjects: HIV infections -- Treatment , HIV (Viruses) , AIDS (Disease) -- Treatment , Nuclear magnetic resonance , Heterocyclic compounds -- Derivatives , Enzyme inhibitors , Chemical inhibitors , Quinoline
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4357 , http://hdl.handle.net/10962/d1005022 , HIV infections -- Treatment , HIV (Viruses) , AIDS (Disease) -- Treatment , Nuclear magnetic resonance , Heterocyclic compounds -- Derivatives , Enzyme inhibitors , Chemical inhibitors , Quinoline
- Description: The project has focused on the preparation of several series of compounds designed as potential HIV-1 integrase inhibitors. Various 2-nitrobenzaldehydes have been reacted with two activated alkenes, methyl vinyl ketone (MVK) and methyl acrylate, under Baylis-Hillman conditions to afford α-methylene-β-hydroxylalkyl derivatives in moderate to excellent yields. The reactions were conducted using the tertiary amine catalysts, 1,4-diazabicyclo[2.2.2]octane(DABCO) or 3-hydroxyquinuclidine (3-HQ) with chloroform as solvent, and yields were optimised by varying the catalyst, reagent concentrations and the reaction time. Reductive cyclization of the Baylis-Hillman adducts via catalytic hydrogenation, using 10% palladiumon-carbon catalyst in ethanol, afforded quinoline and quinoline N-oxide derivatives. In some cases “acyclic” reduction products were also isolated. Reaction of the Baylis-Hillman MVK adducts with HCl, has resulted in effective nucleophilic (SN’) displacement of the hydroxyl group to afford allylic chloride derivatives. Direct substitution of these chloro derivatives by secondary or primary amines, followed by catalytic hydrogenation gave quinoline derivatives containing a 3-aminomethyl substituent. The Baylis-Hillman ester adducts obtained from reaction with methyl acrylate were treated directly with various amines to give diastereomeric conjugate addition products. Reactions with piperazine gave N,N’-disubstituted piperazine products. The piperidine derivatives have been dehydrated to give cinnamate esters in moderate yields. The products, which have all been satisfactorily characterised by elemental (HRMS) and spectroscopic (1- and 2-D NMR) analysis, constitute a “library” of compounds for in silico and in vitro studies as potential HIV integrase inhibitors.
- Full Text:
- Date Issued: 2010
Synthesis, characterization and reactions of novel ferrocenylimidazoles as donor ligands
- Authors: Onyancha, Douglas Okerio
- Date: 2010
- Subjects: Ferrocene
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10390 , http://hdl.handle.net/10948/1150 , Ferrocene
- Description: In this project a series of ferrocenylimidazole derivatives were successfully prepared and characterized using an array of analytical techniques. Reactions of ferrocenylcarbinols with N,N′-thiocarbonyldiimidazole under both solvent-free conditions and in dichloromethane are described. The reaction of ferrocenylmethanol afforded S,S-bis(ferrocenylmethyl)dithiocarbonate, the reaction of α-substituted ferrocenylcarbinols provided ferrocenylalkylimidazolides, while ω-ferrocenylcarbinols yielded ferrocenylimidazolecarbothioates. The reactions were carried out under solvent-free conditions, consistent with the principles of Green Chemistry. Ferrocenyl benzyl ethers were successfully prepared by reacting 4-ferrocenylbenzyl-1Hcarboxylate with a series of primary alcohols under catalytic condition and under a catalyst– free environment. Refluxing a mixture of alcohol-water and 4-ferrocenylbenzyl-1Hcarboxylate provided the corresponding ethers in modest yields. The same ethers were obtained at room temperature by employing potassium tetrachloroplatinate or hydrochloric acid as catalyst. Ferrocenyl-1H-imidazole, 4-ferrocenylphenyl-1H-imidazole and their corresponding ferrocenyl-3-subsitituted imidazolium salts have been successfully synthesized. The compounds were characterized and the electrochemical properties of selected imidazolium salts were examined by cyclic voltammetry. Additionally, X-ray structures of two of the imidazolium salts were determined. The imidazolium salts were found to be good catalysts for the Heck and Suzuki cross-coupling reactions.
- Full Text:
- Date Issued: 2010
- Authors: Onyancha, Douglas Okerio
- Date: 2010
- Subjects: Ferrocene
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10390 , http://hdl.handle.net/10948/1150 , Ferrocene
- Description: In this project a series of ferrocenylimidazole derivatives were successfully prepared and characterized using an array of analytical techniques. Reactions of ferrocenylcarbinols with N,N′-thiocarbonyldiimidazole under both solvent-free conditions and in dichloromethane are described. The reaction of ferrocenylmethanol afforded S,S-bis(ferrocenylmethyl)dithiocarbonate, the reaction of α-substituted ferrocenylcarbinols provided ferrocenylalkylimidazolides, while ω-ferrocenylcarbinols yielded ferrocenylimidazolecarbothioates. The reactions were carried out under solvent-free conditions, consistent with the principles of Green Chemistry. Ferrocenyl benzyl ethers were successfully prepared by reacting 4-ferrocenylbenzyl-1Hcarboxylate with a series of primary alcohols under catalytic condition and under a catalyst– free environment. Refluxing a mixture of alcohol-water and 4-ferrocenylbenzyl-1Hcarboxylate provided the corresponding ethers in modest yields. The same ethers were obtained at room temperature by employing potassium tetrachloroplatinate or hydrochloric acid as catalyst. Ferrocenyl-1H-imidazole, 4-ferrocenylphenyl-1H-imidazole and their corresponding ferrocenyl-3-subsitituted imidazolium salts have been successfully synthesized. The compounds were characterized and the electrochemical properties of selected imidazolium salts were examined by cyclic voltammetry. Additionally, X-ray structures of two of the imidazolium salts were determined. The imidazolium salts were found to be good catalysts for the Heck and Suzuki cross-coupling reactions.
- Full Text:
- Date Issued: 2010
Comparison of A₄ neutrino mass models
- Barry, James Munnik Hamilton
- Authors: Barry, James Munnik Hamilton
- Date: 2010
- Subjects: Neutrinos -- Mass , Standard model (Nuclear physics) , Particles (Nuclear physics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5554 , http://hdl.handle.net/10962/d1015271
- Description: The present neutrino oscillation data are compatible with tri-bimaximal mixing, to leading order. The addition of an A₄ family symmetry and extended Higgs sector to the Standard Model can generate this mixing pattern, assuming the correct vacuum expectation value alignment of Higgs scalars. The effect of deviating this alignment is studied, for different types of A₄ models, with a phenomenological emphasis: the effect of perturbations on the model predictions for the neutrino oscillation and neutrino mass observables. The standard theoretical description of neutrino oscillations is presented, along with a summary of the past, present and future experimental efforts aimed at measuring the neutrino mixing parameters. Additionally, the current constraints on the sum of absolute neutrino masses and the amplitude for neutrinoless double beta decay, which is yet to be observed, are discussed. These constraints provide a model-independent test of family symmetery models. The Standard Model is reviewed, and extensions to the Standard Model such as the seesaw mechanism(s) are discussed: these are designed to endow neutrinos with mass, and can be incorporated into A₄ symmetry models. Models with different A₄ particle assignments are analysed for deviations from tribimaximal mixing. There are nine models presented in Chapter 5, with lepton doublets transforming as 3 (underlined) and right-handed charged leptons transforming as 1, 1', 1" (all underlined) ; five of these include right-handed neutrinos transforming as 3 (underlined) and make use of the seesaw mechanism. Chapter 6 contains the analysis of six models that assign all leptons to the 3 (underlined) representation, with four of these utilising the seesaw mechanism. The models are tested for any degree of fine tuning of the parameters that define the mass matrices. The effect of perturbations on the mixing angle observables, in particular sin² ∅₁₃ and sin² ∅₂₃, is studied, as well as the effect on the Jarlskog invariant, Jcp. Investigations of the (Mee)- ∑Mv parameter space allow for comparison with current data, and can lead to the possible exclusion of a particular model by constraints from future data.
- Full Text:
- Date Issued: 2010
- Authors: Barry, James Munnik Hamilton
- Date: 2010
- Subjects: Neutrinos -- Mass , Standard model (Nuclear physics) , Particles (Nuclear physics)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5554 , http://hdl.handle.net/10962/d1015271
- Description: The present neutrino oscillation data are compatible with tri-bimaximal mixing, to leading order. The addition of an A₄ family symmetry and extended Higgs sector to the Standard Model can generate this mixing pattern, assuming the correct vacuum expectation value alignment of Higgs scalars. The effect of deviating this alignment is studied, for different types of A₄ models, with a phenomenological emphasis: the effect of perturbations on the model predictions for the neutrino oscillation and neutrino mass observables. The standard theoretical description of neutrino oscillations is presented, along with a summary of the past, present and future experimental efforts aimed at measuring the neutrino mixing parameters. Additionally, the current constraints on the sum of absolute neutrino masses and the amplitude for neutrinoless double beta decay, which is yet to be observed, are discussed. These constraints provide a model-independent test of family symmetery models. The Standard Model is reviewed, and extensions to the Standard Model such as the seesaw mechanism(s) are discussed: these are designed to endow neutrinos with mass, and can be incorporated into A₄ symmetry models. Models with different A₄ particle assignments are analysed for deviations from tribimaximal mixing. There are nine models presented in Chapter 5, with lepton doublets transforming as 3 (underlined) and right-handed charged leptons transforming as 1, 1', 1" (all underlined) ; five of these include right-handed neutrinos transforming as 3 (underlined) and make use of the seesaw mechanism. Chapter 6 contains the analysis of six models that assign all leptons to the 3 (underlined) representation, with four of these utilising the seesaw mechanism. The models are tested for any degree of fine tuning of the parameters that define the mass matrices. The effect of perturbations on the mixing angle observables, in particular sin² ∅₁₃ and sin² ∅₂₃, is studied, as well as the effect on the Jarlskog invariant, Jcp. Investigations of the (Mee)- ∑Mv parameter space allow for comparison with current data, and can lead to the possible exclusion of a particular model by constraints from future data.
- Full Text:
- Date Issued: 2010
Historical biogeography of the tribe Platypleurini Schmidt, 1918 (Hemiptera: Cicadidae) with a focus on Southern Africa
- Authors: Price, Benjamin Wills
- Date: 2010
- Subjects: Biogeography -- History -- Africa, Southern Cicadas -- Africa, Southern Cicada (Genus) -- Africa, Southern Biodiversity -- Africa, Southern Cicadas -- Variation -- Africa, Southern
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5708 , http://hdl.handle.net/10962/d1005394
- Description: With our contemporary biota under increasing threat of extinction, it is of interest to understand where, why and how biological diversity is generated. If focussed on appropriate taxa, phylogeographic and phylogenetic studies can assist in the identification of both places and processes central to the origin and maintenance of biological diversity. It is explained why southern Africa presents a perfect test-bed for exploring such mechanisms of diversification and why cicadas (Hemiptera: Cicadidae) have proved very suitable tools for studies of historical biogeography. This study then exemplifies these points by providing the first large-scale investigation of the historical biogeography of the tribe Platypleurini Schmidt, 1918, with emphasis on the genus Platypleura Amyot & Seville, 1843 in southern Africa. Standard methods of DNA sequencing provided data from portions of the mitochondrial small subunit ribosomal 16S RNA (16S) and cytochrome oxidase subunits I (COI) and II (COII); and the nuclear elongation factor 1 alpha (EF-1α) from 400 ethanol-preserved specimens. These data were analysed using standard phylogenetic methods and a time scale of diversification was estimated using a Bayesian framework and both fossil data and DNA substitution rates. The results showed that the tribe is too recent to be of Gondwanan origin. The lack of monophyly of the genera represented in both Asia and Africa showed that the tribe needs formal taxonomic revision. Diversification of the African platypleurine genera coincides with aridification in the early Oligocene. Dispersal of Asian platypleurine taxa coincides with the meeting of Africa and Eurasia in the mid-Oligocene. Two radiations within African Platypleura are hypothesised; one distributed over most of sub-Saharan Africa and the second restricted to southern Africa, with clades restricted within regional biomes. Within each of the three focal biomes, cryptic taxonomic diversity was confirmed, suggesting that, even in relatively well understood groups such as the southern African platypleurine cicadas, molecular data can identify further diversity. Although each focal taxon was restricted to non-overlapping biomes, comparison of the three biomes highlighted interactions between palaeoclimates and fixed landscape features (coastal topography, river catchments and escarpments) as causative agents of vicariance, dispersal, extinction and diversification of these volant insects. The results of using co-distributed species for comparative study cautions against making inferences based on single-taxon datasets and highlights the need to use many, evolutionarily independent taxa when identifying mechanisms of diversification. The dating analyses imply that within-species lineage diversification occurred overwhelmingly within the Pleistocene, a trend that is being increasingly recognised in print for other biota. Some caveats about using phylogenetic approaches to estimate ancestral areas are illustrated. Several recommendations are made regarding additional taxa and data sources for understanding the origin and maintenance of biological diversity.
- Full Text:
- Date Issued: 2010
- Authors: Price, Benjamin Wills
- Date: 2010
- Subjects: Biogeography -- History -- Africa, Southern Cicadas -- Africa, Southern Cicada (Genus) -- Africa, Southern Biodiversity -- Africa, Southern Cicadas -- Variation -- Africa, Southern
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5708 , http://hdl.handle.net/10962/d1005394
- Description: With our contemporary biota under increasing threat of extinction, it is of interest to understand where, why and how biological diversity is generated. If focussed on appropriate taxa, phylogeographic and phylogenetic studies can assist in the identification of both places and processes central to the origin and maintenance of biological diversity. It is explained why southern Africa presents a perfect test-bed for exploring such mechanisms of diversification and why cicadas (Hemiptera: Cicadidae) have proved very suitable tools for studies of historical biogeography. This study then exemplifies these points by providing the first large-scale investigation of the historical biogeography of the tribe Platypleurini Schmidt, 1918, with emphasis on the genus Platypleura Amyot & Seville, 1843 in southern Africa. Standard methods of DNA sequencing provided data from portions of the mitochondrial small subunit ribosomal 16S RNA (16S) and cytochrome oxidase subunits I (COI) and II (COII); and the nuclear elongation factor 1 alpha (EF-1α) from 400 ethanol-preserved specimens. These data were analysed using standard phylogenetic methods and a time scale of diversification was estimated using a Bayesian framework and both fossil data and DNA substitution rates. The results showed that the tribe is too recent to be of Gondwanan origin. The lack of monophyly of the genera represented in both Asia and Africa showed that the tribe needs formal taxonomic revision. Diversification of the African platypleurine genera coincides with aridification in the early Oligocene. Dispersal of Asian platypleurine taxa coincides with the meeting of Africa and Eurasia in the mid-Oligocene. Two radiations within African Platypleura are hypothesised; one distributed over most of sub-Saharan Africa and the second restricted to southern Africa, with clades restricted within regional biomes. Within each of the three focal biomes, cryptic taxonomic diversity was confirmed, suggesting that, even in relatively well understood groups such as the southern African platypleurine cicadas, molecular data can identify further diversity. Although each focal taxon was restricted to non-overlapping biomes, comparison of the three biomes highlighted interactions between palaeoclimates and fixed landscape features (coastal topography, river catchments and escarpments) as causative agents of vicariance, dispersal, extinction and diversification of these volant insects. The results of using co-distributed species for comparative study cautions against making inferences based on single-taxon datasets and highlights the need to use many, evolutionarily independent taxa when identifying mechanisms of diversification. The dating analyses imply that within-species lineage diversification occurred overwhelmingly within the Pleistocene, a trend that is being increasingly recognised in print for other biota. Some caveats about using phylogenetic approaches to estimate ancestral areas are illustrated. Several recommendations are made regarding additional taxa and data sources for understanding the origin and maintenance of biological diversity.
- Full Text:
- Date Issued: 2010
An investigation into the readability of the grade 10 physical science textbooks : a case study
- Authors: Van Heerden, Lesley Lynne
- Date: 2010
- Subjects: Textbooks -- South Africa -- Readability , Readability (Literary style) , Science -- Study and teaching (Secondary) -- Case studies
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1993 , http://hdl.handle.net/10962/d1013365
- Description: In her newsletter “Curriculum News, Improving the Quality of Learning and Teaching: Planning for 2010 and Beyond”, Mrs Angie Motshekga, MP, Minister of Basic Education, positions the textbook very definitely as central to the curriculum and states that it is one of the most effective tools through which to deliver the curriculum and support assessment. Acknowledging the importance of the accessibility of textbooks for the South African classroom audience, this study has sought to investigate the readability of the chemistry section of grade 10 science textbooks. Readability research is concerned with the relationship between the textbook, the reader and the context in which the book is read; research supports the use of both classical quantitative measures and a qualitative cognitive-structural form of analysis to investigate this relationship. The research design is a mixed method one where quantitative and qualitative data were collected simultaneously: the methodical application of selected readability formulae gave rise to quantitative data while the line-by-line textual analysis, tracing cognitive-structural aspects, and focus-group discussions with teachers gave rise to the qualitative data. The results of the merged data analysis were then interpreted together to provide a better understanding of the readability of the texts for a South African audience. The results of the investigation reveal that readability is greatly impaired for a number of reasons, the primary one being a lack of articulation between the textbook writers/editors and the audience for which they are writing and preparing the texts. This is particularly reflected in the inadequate preparation of the material for the English Second Language reader, as certain textbooks are completely out of their reach. Furthermore, this lack of articulation can be traced to the lack of time available for piloting the textbooks: an invaluable intervention in the process of textbook production.
- Full Text:
- Date Issued: 2010
- Authors: Van Heerden, Lesley Lynne
- Date: 2010
- Subjects: Textbooks -- South Africa -- Readability , Readability (Literary style) , Science -- Study and teaching (Secondary) -- Case studies
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:1993 , http://hdl.handle.net/10962/d1013365
- Description: In her newsletter “Curriculum News, Improving the Quality of Learning and Teaching: Planning for 2010 and Beyond”, Mrs Angie Motshekga, MP, Minister of Basic Education, positions the textbook very definitely as central to the curriculum and states that it is one of the most effective tools through which to deliver the curriculum and support assessment. Acknowledging the importance of the accessibility of textbooks for the South African classroom audience, this study has sought to investigate the readability of the chemistry section of grade 10 science textbooks. Readability research is concerned with the relationship between the textbook, the reader and the context in which the book is read; research supports the use of both classical quantitative measures and a qualitative cognitive-structural form of analysis to investigate this relationship. The research design is a mixed method one where quantitative and qualitative data were collected simultaneously: the methodical application of selected readability formulae gave rise to quantitative data while the line-by-line textual analysis, tracing cognitive-structural aspects, and focus-group discussions with teachers gave rise to the qualitative data. The results of the merged data analysis were then interpreted together to provide a better understanding of the readability of the texts for a South African audience. The results of the investigation reveal that readability is greatly impaired for a number of reasons, the primary one being a lack of articulation between the textbook writers/editors and the audience for which they are writing and preparing the texts. This is particularly reflected in the inadequate preparation of the material for the English Second Language reader, as certain textbooks are completely out of their reach. Furthermore, this lack of articulation can be traced to the lack of time available for piloting the textbooks: an invaluable intervention in the process of textbook production.
- Full Text:
- Date Issued: 2010
Population biology and aspects of the socio-spatial organisation of the woodland dormouse Graphiurus Murinus (Desmaret, 1822) in the Great Fish River Reserve, South Africa
- Madikiza, Zimkitha Josephine Kimberly
- Authors: Madikiza, Zimkitha Josephine Kimberly
- Date: 2010
- Subjects: Dormice , Mice , Muridae , Spatial behavior , Territoriality (Zoology) , Crowding stress
- Language: English
- Type: Thesis , Masters , MSc (Zoology)
- Identifier: vital:11788 , http://hdl.handle.net/10353/443 , Dormice , Mice , Muridae , Spatial behavior , Territoriality (Zoology) , Crowding stress
- Description: The population biology and socio-spatial organisation of the woodland dormouse, Graphiurus murinus (Desmarest, 1822), was investigated in a riverine forest at the Great Fish River Reserve (GFRR), South Africa. Data were collected by means of a monthly live trapping and nestbox monitoring programme. Between February 2006 and June 2007, 75 woodland dormice were trapped and/or found in nestboxes and marked: these were 39 adults (13 males, 21 females, five undetermined) and 36 juveniles (five males, 14 females, 17 undetermined). The population showed a steady increase from June 2006–November 2006 and a peak in December 2006–January 2007 as a result of the influx of juveniles. The minimum number of dormice known to be alive (MNA) varied between 40 in December 2006– January 2007 (summer), and a low of three in June 2007 (winter). The range in population density was therefore between 1.2 and 16 dormice per ha. Winter mortality and/or spring dispersal accounted for the disappearance of 55 percent of juveniles. The overall annual adult:juvenile ratio was 1.08. The overall sex ratio was 1.94 female per one male. In females, reproductive activity was observed from September 2006 to end January 2007. The pattern observed in males was similar, as dormice with descended testes were exclusively found from October to end January. Females gave birth during the second half of October to beginning of February. Litters (n = 11) consisted of an average (± SD) 3.73 ± 0.47 young. Over the study period, 27 dormice were trapped or found in nestboxes more than eight times, thus allowing me to estimate their home range size and the spatial overlap between these individuals. On average, dormouse home range size was 2,514 m2 (range: 319 – 4,863 m2). No difference was recorded between one-year old adults and older adults, or between all adults and juveniles. However, adult male dormice (3,989 m2, n = 5) had home ranges almost twice as large as females (2,091 m2, n = 9). No similar trend was found in juveniles. Intrasexual home range overlap was on average 62 percent in adult males, and 26 percent in adult females. However, females overlapped with more neighbouring female home ranges than did males with neighbouring male home ranges, so that, as for males, only small parts of female home ranges were really exclusive. On average, males overlapped a larger Abstract Ecology of woodland dormice M.Sc. Thesis 16 proportion (48 percent) of female home ranges than did females with neighbouring male home ranges (27 percent). In addition, males overlapped with significantly more female home ranges (7.8) than did females with male home ranges (4.9). Trapping success and nestbox data agree with the socio-ecological model. Females showed increased mobility during summer, more likely to find suitable nesting sites, and food for milk production during the reproductive season. The use of nestboxes, however, was constant throughout the year. In males, both the trapping success and nestbox use were higher during the mating season (spring), when an increased mobility and occupation of nestboxes probably increased the chances to locate and mate with (a) receptive female(s). Hence, food and (artificial) nest sites may constitute an important resource for females, whereas females seem to represent the main resource for males. Although food availability was not determined, a comparison of female and male distribution patterns provided interesting information on the mating system of woodland dormice. In GFRR, the dispersion pattern of female woodland dormice was “rather” clumped, i.e. females were non-territorial. As some females showed a dyadic intrasexual overlap of up to 90 percent, and population density was very high at the study site, this may indicate that food was very abundant and/or renewed rapidly. Based on the wide range of birth dates observed during the study period, females clearly come into oestrus at different times. In such circumstances (asynchronous sexual receptivity in females), the Female in Space and Time Hypothesis (Ims 1987a) predicts that males will be non-territorial and promiscuous. Live-trapping, nestbox use and home range data indeed suggested that male woodland dormice do not defend territories, but search for and aggregate around receptive females during the mating season.
- Full Text:
- Date Issued: 2010
- Authors: Madikiza, Zimkitha Josephine Kimberly
- Date: 2010
- Subjects: Dormice , Mice , Muridae , Spatial behavior , Territoriality (Zoology) , Crowding stress
- Language: English
- Type: Thesis , Masters , MSc (Zoology)
- Identifier: vital:11788 , http://hdl.handle.net/10353/443 , Dormice , Mice , Muridae , Spatial behavior , Territoriality (Zoology) , Crowding stress
- Description: The population biology and socio-spatial organisation of the woodland dormouse, Graphiurus murinus (Desmarest, 1822), was investigated in a riverine forest at the Great Fish River Reserve (GFRR), South Africa. Data were collected by means of a monthly live trapping and nestbox monitoring programme. Between February 2006 and June 2007, 75 woodland dormice were trapped and/or found in nestboxes and marked: these were 39 adults (13 males, 21 females, five undetermined) and 36 juveniles (five males, 14 females, 17 undetermined). The population showed a steady increase from June 2006–November 2006 and a peak in December 2006–January 2007 as a result of the influx of juveniles. The minimum number of dormice known to be alive (MNA) varied between 40 in December 2006– January 2007 (summer), and a low of three in June 2007 (winter). The range in population density was therefore between 1.2 and 16 dormice per ha. Winter mortality and/or spring dispersal accounted for the disappearance of 55 percent of juveniles. The overall annual adult:juvenile ratio was 1.08. The overall sex ratio was 1.94 female per one male. In females, reproductive activity was observed from September 2006 to end January 2007. The pattern observed in males was similar, as dormice with descended testes were exclusively found from October to end January. Females gave birth during the second half of October to beginning of February. Litters (n = 11) consisted of an average (± SD) 3.73 ± 0.47 young. Over the study period, 27 dormice were trapped or found in nestboxes more than eight times, thus allowing me to estimate their home range size and the spatial overlap between these individuals. On average, dormouse home range size was 2,514 m2 (range: 319 – 4,863 m2). No difference was recorded between one-year old adults and older adults, or between all adults and juveniles. However, adult male dormice (3,989 m2, n = 5) had home ranges almost twice as large as females (2,091 m2, n = 9). No similar trend was found in juveniles. Intrasexual home range overlap was on average 62 percent in adult males, and 26 percent in adult females. However, females overlapped with more neighbouring female home ranges than did males with neighbouring male home ranges, so that, as for males, only small parts of female home ranges were really exclusive. On average, males overlapped a larger Abstract Ecology of woodland dormice M.Sc. Thesis 16 proportion (48 percent) of female home ranges than did females with neighbouring male home ranges (27 percent). In addition, males overlapped with significantly more female home ranges (7.8) than did females with male home ranges (4.9). Trapping success and nestbox data agree with the socio-ecological model. Females showed increased mobility during summer, more likely to find suitable nesting sites, and food for milk production during the reproductive season. The use of nestboxes, however, was constant throughout the year. In males, both the trapping success and nestbox use were higher during the mating season (spring), when an increased mobility and occupation of nestboxes probably increased the chances to locate and mate with (a) receptive female(s). Hence, food and (artificial) nest sites may constitute an important resource for females, whereas females seem to represent the main resource for males. Although food availability was not determined, a comparison of female and male distribution patterns provided interesting information on the mating system of woodland dormice. In GFRR, the dispersion pattern of female woodland dormice was “rather” clumped, i.e. females were non-territorial. As some females showed a dyadic intrasexual overlap of up to 90 percent, and population density was very high at the study site, this may indicate that food was very abundant and/or renewed rapidly. Based on the wide range of birth dates observed during the study period, females clearly come into oestrus at different times. In such circumstances (asynchronous sexual receptivity in females), the Female in Space and Time Hypothesis (Ims 1987a) predicts that males will be non-territorial and promiscuous. Live-trapping, nestbox use and home range data indeed suggested that male woodland dormice do not defend territories, but search for and aggregate around receptive females during the mating season.
- Full Text:
- Date Issued: 2010
Metabolic energy relations in the Eastern Cape Angulate Tortoise (Chersina Anguluta)
- Authors: Setlalekgomo, Mpho Rinah
- Date: 2010
- Subjects: Eastern Cape angulate Tortoise , Oxygen consumption (Physiology)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10690 , http://hdl.handle.net/10948/1400 , Eastern Cape angulate Tortoise , Oxygen consumption (Physiology)
- Description: The daily oxygen consumption (VO2) pattern, the effects of varying ambient temperatures, season and mass on the resting oxygen consumption (RVO2) of Chersina angulata of the Eastern Cape were investigated. The RVO2 was measured using flow-through respirometry and specific resting oxygen consumption (sRVO2) calculated. To determine the daily pattern in the VO2 of C. angulata, the tortoises were acclimated in an environmentally controlled room (ECR) to an ambient temperature of 26 ± 1°C and a light regime of 14 hours of light and 10 hours of darkness (14L:10D) for at least a week prior to the RVO2 measurements. The RVO2 was measured at a constant temperature of 26 ± 1°C, and at three different light regimes, namely: 14L:10D, constant darkness (DD) and constant light (LL). There were no significant effects of mass or gender on the sRVO2 of the tortoises used. Rhythms in the sRVO2 were detected under all three light regimes. The amplitudes of the rhythm were largest at 14L:10D, followed by DD and smallest at LL regime. The persistence of the rhythmic pattern under constant conditions suggests the existence of an endogenous circadian rhythm in the sRVO2 for adult C. angulata. To test for the effect of ambient temperature on the sRVO2 of adult C. angulata, the tortoises were acclimated to 22 ± 1°C and a 14L:10D light regime prior to the RVO2 measurements. RVO2 was measured at eight experimental temperatures; 14°C, 18°C, 22°C, 26°C, 30°C, 35°C, 38°C and 40°C. The sRVO2 was not influenced by gender and increased with experimental temperatures, but this did not happen consistently over the whole range of temperatures tested. A plateau, possibly a thermal preferendum zone, was detected within the temperature range of 26 - 38°C. Determination of seasonal effect on the sRVO2 of adult C. angulata was accomplished by acclimating tortoises to standard summer and winter conditions. Seasonal effects were tested in the appropriate seasons. Winter experiments were conducted in winter and summer experiments conducted in summer. The RVO2 was measured at experimental temperature 14°C, 18°C and 22°C. In addition RVO2 of iv winter-acclimated tortoises was also measured at 10°C. The sRVO2 increased significantly with increasing temperature within the temperature range tested. No distinct pattern was observed in the seasonal acclimation of adult C. angulata. The metabolic rate-temperature curves of the summer and the winter-acclimated tortoises cross each other. Season and temperature had no significant effects on the mass-scaling exponent of the sRVO2. The exponent ranged from 0.48 to 0.73 within the temperature range of 22 - 38°C. Below and above this temperature range, the exponent ranged from 1.47 to 1.67. An inverse relationship was observed between sRVO2 and body mass over the temperature range of 22 - 38°C. At 14°C and 18°C, sRVO2 increased with body mass, while at 10°C and at 40°C the slope was 1.01.
- Full Text:
- Date Issued: 2010
- Authors: Setlalekgomo, Mpho Rinah
- Date: 2010
- Subjects: Eastern Cape angulate Tortoise , Oxygen consumption (Physiology)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10690 , http://hdl.handle.net/10948/1400 , Eastern Cape angulate Tortoise , Oxygen consumption (Physiology)
- Description: The daily oxygen consumption (VO2) pattern, the effects of varying ambient temperatures, season and mass on the resting oxygen consumption (RVO2) of Chersina angulata of the Eastern Cape were investigated. The RVO2 was measured using flow-through respirometry and specific resting oxygen consumption (sRVO2) calculated. To determine the daily pattern in the VO2 of C. angulata, the tortoises were acclimated in an environmentally controlled room (ECR) to an ambient temperature of 26 ± 1°C and a light regime of 14 hours of light and 10 hours of darkness (14L:10D) for at least a week prior to the RVO2 measurements. The RVO2 was measured at a constant temperature of 26 ± 1°C, and at three different light regimes, namely: 14L:10D, constant darkness (DD) and constant light (LL). There were no significant effects of mass or gender on the sRVO2 of the tortoises used. Rhythms in the sRVO2 were detected under all three light regimes. The amplitudes of the rhythm were largest at 14L:10D, followed by DD and smallest at LL regime. The persistence of the rhythmic pattern under constant conditions suggests the existence of an endogenous circadian rhythm in the sRVO2 for adult C. angulata. To test for the effect of ambient temperature on the sRVO2 of adult C. angulata, the tortoises were acclimated to 22 ± 1°C and a 14L:10D light regime prior to the RVO2 measurements. RVO2 was measured at eight experimental temperatures; 14°C, 18°C, 22°C, 26°C, 30°C, 35°C, 38°C and 40°C. The sRVO2 was not influenced by gender and increased with experimental temperatures, but this did not happen consistently over the whole range of temperatures tested. A plateau, possibly a thermal preferendum zone, was detected within the temperature range of 26 - 38°C. Determination of seasonal effect on the sRVO2 of adult C. angulata was accomplished by acclimating tortoises to standard summer and winter conditions. Seasonal effects were tested in the appropriate seasons. Winter experiments were conducted in winter and summer experiments conducted in summer. The RVO2 was measured at experimental temperature 14°C, 18°C and 22°C. In addition RVO2 of iv winter-acclimated tortoises was also measured at 10°C. The sRVO2 increased significantly with increasing temperature within the temperature range tested. No distinct pattern was observed in the seasonal acclimation of adult C. angulata. The metabolic rate-temperature curves of the summer and the winter-acclimated tortoises cross each other. Season and temperature had no significant effects on the mass-scaling exponent of the sRVO2. The exponent ranged from 0.48 to 0.73 within the temperature range of 22 - 38°C. Below and above this temperature range, the exponent ranged from 1.47 to 1.67. An inverse relationship was observed between sRVO2 and body mass over the temperature range of 22 - 38°C. At 14°C and 18°C, sRVO2 increased with body mass, while at 10°C and at 40°C the slope was 1.01.
- Full Text:
- Date Issued: 2010
Generation of polyclonal antibodies against Theiler's Murine Encephalomyelitis virus protein 2C, and their use in investigating localisation of the protein in infected cells
- Authors: Jauka, Tembisa Innocencia
- Date: 2010
- Subjects: Picornaviruses , RNA viruses , Immunoglobulins , Encephalomyelitis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3959 , http://hdl.handle.net/10962/d1004018 , Picornaviruses , RNA viruses , Immunoglobulins , Encephalomyelitis
- Description: The Picornavirus family of positive sense RNA viruses includes some significant human and animal pathogens including Poliovirus (PV), Foot-and-Mouth disease virus (FMDV) and Human Rhinovirus (HRV). The genome is translated within the host cell into a polyprotein that is proteolytically cleaved into the structural and nonstructural proteins. The highly conserved, non-structural protein 2C has numerous roles during the virus life cycle and is essential for virus replication. Although the protein has been well studied in the case of PV, its interactions with the host cell during picornavirus infection is poorly understood. Theiler’s Encephalomyelitis virus (TMEV) is a picornavirus that infects mice, and is being used in our laboratory as a model in which to study the 2C protein. In this study, polyclonal antibodies against the TMEV 2C protein were generated and used to localise the protein in infected cells by indirect immunofluorescence. To produce antigen for immunisation purposes, the TMEV-2C protein sequence was analysed to identify hydrophilic and antigenic regions. An internal region of the 2C representing amino acid residues 31-210 was selected, expressed in bacteria and purified by nickel NTA affinity chromatography. Time course analysis of 2C (31-210) showed that the peptide was maximally expressed at 5 hours post induction. The peptide was solubilised using a mild detergent and 1.5 mg of purified antigen was used for immunisation of rabbits. Western blot analysis confirmed that the antibodies could detect both bacteriallyexpressed antigen, and virally-expressed 2C. Examination of virus-infected baby hamster kidney cells by immunofluorescence and confocal microscopy using the antiserum (anti-TMEV 2C antibodies) showed that the protein had a diffuse distribution upon early infection and at later stages it was located in a large perinuclear structure representing the viral replication complex. Furthermore, 2C localised to the Golgi apparatus as revealed by dual-label immunofluorescence using anti-TMEV 2C antibodies and wheat germ agglutinin (WGA). Furthermore, it was shown that TMEV infection results in changes in cell morphology and a redistribution of the cytoskeletal protein, β-actin. The successful production of antibodies that recognise TMEV 2C opens the way for further studies to investigate interactions between 2C and hostencoded factors.
- Full Text:
- Date Issued: 2010
- Authors: Jauka, Tembisa Innocencia
- Date: 2010
- Subjects: Picornaviruses , RNA viruses , Immunoglobulins , Encephalomyelitis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3959 , http://hdl.handle.net/10962/d1004018 , Picornaviruses , RNA viruses , Immunoglobulins , Encephalomyelitis
- Description: The Picornavirus family of positive sense RNA viruses includes some significant human and animal pathogens including Poliovirus (PV), Foot-and-Mouth disease virus (FMDV) and Human Rhinovirus (HRV). The genome is translated within the host cell into a polyprotein that is proteolytically cleaved into the structural and nonstructural proteins. The highly conserved, non-structural protein 2C has numerous roles during the virus life cycle and is essential for virus replication. Although the protein has been well studied in the case of PV, its interactions with the host cell during picornavirus infection is poorly understood. Theiler’s Encephalomyelitis virus (TMEV) is a picornavirus that infects mice, and is being used in our laboratory as a model in which to study the 2C protein. In this study, polyclonal antibodies against the TMEV 2C protein were generated and used to localise the protein in infected cells by indirect immunofluorescence. To produce antigen for immunisation purposes, the TMEV-2C protein sequence was analysed to identify hydrophilic and antigenic regions. An internal region of the 2C representing amino acid residues 31-210 was selected, expressed in bacteria and purified by nickel NTA affinity chromatography. Time course analysis of 2C (31-210) showed that the peptide was maximally expressed at 5 hours post induction. The peptide was solubilised using a mild detergent and 1.5 mg of purified antigen was used for immunisation of rabbits. Western blot analysis confirmed that the antibodies could detect both bacteriallyexpressed antigen, and virally-expressed 2C. Examination of virus-infected baby hamster kidney cells by immunofluorescence and confocal microscopy using the antiserum (anti-TMEV 2C antibodies) showed that the protein had a diffuse distribution upon early infection and at later stages it was located in a large perinuclear structure representing the viral replication complex. Furthermore, 2C localised to the Golgi apparatus as revealed by dual-label immunofluorescence using anti-TMEV 2C antibodies and wheat germ agglutinin (WGA). Furthermore, it was shown that TMEV infection results in changes in cell morphology and a redistribution of the cytoskeletal protein, β-actin. The successful production of antibodies that recognise TMEV 2C opens the way for further studies to investigate interactions between 2C and hostencoded factors.
- Full Text:
- Date Issued: 2010
Development of a stability-indicating high performance liquid chromatographic method for the analysis of topiramate and dissolution rate testing in topiramate tablets
- Mohammadi, Ali, Rezanour, Nasrin, Ansari Dogaheh, M, Walker, Roderick B
- Authors: Mohammadi, Ali , Rezanour, Nasrin , Ansari Dogaheh, M , Walker, Roderick B
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:6412 , http://hdl.handle.net/10962/d1006507
- Description: A stability-indicating high performance liquid chromatographic(HPLC) method was developed and validated for the quantitation and dissolution determination of topiramate in tablet dosage forms. An isocratic separation was achieved using a phenyl column with a flow rate of 1 mL/min using UV detection at 264 nm. Topiramate has low UV absorbtivity and was subjected to derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl). The mobile phase for the separation consisted of acetonitrile: 50 mM sodium dihydrogen phosphate(NaH2PO4) containing 3 % v/v triethylamine (pH 2.8) in a 48:52 v/v ratio. Topiramate was subjected to oxidation, hydrolysis, photolysis and heat for the purposes of stress testing. Separation was achieved for the parent compound and all the degradation products in an overall analytical run time of approximately 15 min with the parent compound topiramate eluting at approximately 9.2 min. The method was linear over the concentration range of 1-100 μg/mL (r = 0.9996) with limits of quantitation and detection of 1 and 0.3 μg/mL, respectively.
- Full Text:
- Date Issued: 2010
- Authors: Mohammadi, Ali , Rezanour, Nasrin , Ansari Dogaheh, M , Walker, Roderick B
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:6412 , http://hdl.handle.net/10962/d1006507
- Description: A stability-indicating high performance liquid chromatographic(HPLC) method was developed and validated for the quantitation and dissolution determination of topiramate in tablet dosage forms. An isocratic separation was achieved using a phenyl column with a flow rate of 1 mL/min using UV detection at 264 nm. Topiramate has low UV absorbtivity and was subjected to derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl). The mobile phase for the separation consisted of acetonitrile: 50 mM sodium dihydrogen phosphate(NaH2PO4) containing 3 % v/v triethylamine (pH 2.8) in a 48:52 v/v ratio. Topiramate was subjected to oxidation, hydrolysis, photolysis and heat for the purposes of stress testing. Separation was achieved for the parent compound and all the degradation products in an overall analytical run time of approximately 15 min with the parent compound topiramate eluting at approximately 9.2 min. The method was linear over the concentration range of 1-100 μg/mL (r = 0.9996) with limits of quantitation and detection of 1 and 0.3 μg/mL, respectively.
- Full Text:
- Date Issued: 2010
Enhancing the saccharolytic phase of sugar beet pulp via hemicellulase synergy
- Authors: Dredge, Roselyn Ann
- Date: 2010
- Subjects: Sugar plantations , Sugar plantations -- South Africa , Sugar beet industry -- South Africa , Saccharomyces cerevisiae -- Biotechnology , Biomass energy industries -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3955 , http://hdl.handle.net/10962/d1004014 , Sugar plantations , Sugar plantations -- South Africa , Sugar beet industry -- South Africa , Saccharomyces cerevisiae -- Biotechnology , Biomass energy industries -- South Africa
- Description: The sugar beet (Beta vulgaris) plant has in recent years been added to the Biofuel Industrial Strategy (Department of Minerals and Energy, 2007) by the South African government as a crop grown for the production of bio-ethanol. Sugar beet is commonly grown in Europe for the production of sucrose and has recently been cultivated in Cradock and the surrounding areas (Engineering News, 2008). The biofuel industry usually ferments the sucrose with Saccharomyces cerevisiae to yield bio-ethanol. However, researchers are presented with a critical role to increase current yields as there are concerns over the process costs from industrial biotechnologists. The beet factories produce a pulp by-product removed of all sucrose. The hemicellulose-rich pulp can be degraded by microbial enzymes to simple sugars that can be subsequently fermented to bio-ethanol. Thus, the pulp represents a potential source for second generation biofuel. The process of utilising microbial hemicellulases requires an initial chemical pre-treatment step to delignify the sugar beet pulp (SBP). An alkaline pre-treatment with ‘slake lime’ (calcium hydroxide) was investigated using a 23 factorial design and the factors examined were: lime load; temperature and time. The analysed results showed the highest release of reducing sugars at the pre-treatment conditions of: 0.4 g lime / g SBP; 40°C and 36 hours. A partial characterisation of the Clostridium cellulovorans hemicellulases was carried out to verify the optimal activity conditions stated in literature. The highest release of reducing sugars was measured at pH 6.5 – 7.0 and at 45°C for arabinofuranosidase A (ArfA); at pH 5.5 and 40°C for mannanase A (ManA) and pH 5.0 – 6.0 and 45°C for xylanase A (XynA). Temperature studies showed that a complete loss of enzymatic activity occurred after 11 hours for ManA; and 84-96 hours for ArfA. XynA was still active after 120 hours. The optimised lime pre-treated SBP was subsequently degraded using various combinations and percentages of C. cellulovorans ArfA, ManA and XynA to determine the maximal release of reducing sugars. Synergistically, the highest synergy was observed at 75% ArfA and 25% ManA, with a specific activity of 2.9 μmol/min/g protein. However, the highest release of sugars was observed at 4.2 μmol/min/g protein at 100% ArfA. This study has initiated the research within South Africa on SBP and its degradation by C. cellulovorans. Preliminary studies show that SBP has the potential to be utilised as a second generation biofuel source.
- Full Text:
- Date Issued: 2010
- Authors: Dredge, Roselyn Ann
- Date: 2010
- Subjects: Sugar plantations , Sugar plantations -- South Africa , Sugar beet industry -- South Africa , Saccharomyces cerevisiae -- Biotechnology , Biomass energy industries -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3955 , http://hdl.handle.net/10962/d1004014 , Sugar plantations , Sugar plantations -- South Africa , Sugar beet industry -- South Africa , Saccharomyces cerevisiae -- Biotechnology , Biomass energy industries -- South Africa
- Description: The sugar beet (Beta vulgaris) plant has in recent years been added to the Biofuel Industrial Strategy (Department of Minerals and Energy, 2007) by the South African government as a crop grown for the production of bio-ethanol. Sugar beet is commonly grown in Europe for the production of sucrose and has recently been cultivated in Cradock and the surrounding areas (Engineering News, 2008). The biofuel industry usually ferments the sucrose with Saccharomyces cerevisiae to yield bio-ethanol. However, researchers are presented with a critical role to increase current yields as there are concerns over the process costs from industrial biotechnologists. The beet factories produce a pulp by-product removed of all sucrose. The hemicellulose-rich pulp can be degraded by microbial enzymes to simple sugars that can be subsequently fermented to bio-ethanol. Thus, the pulp represents a potential source for second generation biofuel. The process of utilising microbial hemicellulases requires an initial chemical pre-treatment step to delignify the sugar beet pulp (SBP). An alkaline pre-treatment with ‘slake lime’ (calcium hydroxide) was investigated using a 23 factorial design and the factors examined were: lime load; temperature and time. The analysed results showed the highest release of reducing sugars at the pre-treatment conditions of: 0.4 g lime / g SBP; 40°C and 36 hours. A partial characterisation of the Clostridium cellulovorans hemicellulases was carried out to verify the optimal activity conditions stated in literature. The highest release of reducing sugars was measured at pH 6.5 – 7.0 and at 45°C for arabinofuranosidase A (ArfA); at pH 5.5 and 40°C for mannanase A (ManA) and pH 5.0 – 6.0 and 45°C for xylanase A (XynA). Temperature studies showed that a complete loss of enzymatic activity occurred after 11 hours for ManA; and 84-96 hours for ArfA. XynA was still active after 120 hours. The optimised lime pre-treated SBP was subsequently degraded using various combinations and percentages of C. cellulovorans ArfA, ManA and XynA to determine the maximal release of reducing sugars. Synergistically, the highest synergy was observed at 75% ArfA and 25% ManA, with a specific activity of 2.9 μmol/min/g protein. However, the highest release of sugars was observed at 4.2 μmol/min/g protein at 100% ArfA. This study has initiated the research within South Africa on SBP and its degradation by C. cellulovorans. Preliminary studies show that SBP has the potential to be utilised as a second generation biofuel source.
- Full Text:
- Date Issued: 2010
Metallophthalocyanines as electrocatalysts and superoxide dismutase mimics
- Authors: Matemadombo, Fungisai
- Date: 2010
- Subjects: Mimicry (Chemistry) Electrocatalysis Superoxide dismutase Electrochemistry Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4325 , http://hdl.handle.net/10962/d1004985
- Description: Syntheses, spectral, electrochemical, and spectroelectrochemical studies of iron, cobalt, and manganese phthalocyanines are reported. The novel coordination of cobalt tetracarboxy metallophthalocyanine to an electrode premodified with aryl radicals and its use in the detection of thiocyanate are reported. This work describes the catalytic activity of cobalt phthalocyanine (CoPc) derivatives adsorbed onto glassy carbon electrodes for the electrocatalytical detection of nitrite, Lcysteine, and melatonin. The modified electrodes efficiently detected nitrite. The CoPc derivative modified electrodes proficiently detected L-cysteine whereas an un-modified electrode could not. This work presents the innovative electrochemical detection of melatonin using electrodes adsorbed with CoPc derivatives. These electrodes detected melatonin at more favorable electrochemical parameters relative to an un-modified gold electrode. The limits of melatonin detection of the modified electrodes lay in the 10⁻⁷ to 10⁻⁶ M region. The modified electrodes accurately detected capsule melatonin concentrations as specified by the supplier and could differentiate between a mixture of melatonin, tryptophan, and ascorbic acid. They reliably detected nitrite, L-cysteine, and melatonin in the 10⁻⁴ to 10⁻² M region. Metallophthalocyanine complexes substituted with thio groups were employed as self assembled monolayers (SAMs). Voltammetry, impedance, atomic force microscopy, and scanning electrochemical microscopy proved that the SAMs all act as selective and efficient barriers to ion permeability. All the SAMs in this work can be used as effective electrochemical sensors of nitrite and L-cysteine in the 10⁻⁴ to 10⁻² M region with competitive limits of detection whereas an un-modified electrode cannot detect Lcysteine. The manganese phthalocyanine SAM modified electrodes are arguably better nitrite and L-cysteine electrocatalysts relative to their iron and cobalt counterparts. Manganese phthalocyanines were used as superoxide dismutase (SOD) mimics. All manganese phthalocyanine complexes in this work acted as SOD mimics in an enzymatic system of superoxide production. From cellular studies, complexes 6d, 6e, 8d, 8e act as intracellular SOD mimics and are without significantly high cellular toxicity.
- Full Text:
- Date Issued: 2010
- Authors: Matemadombo, Fungisai
- Date: 2010
- Subjects: Mimicry (Chemistry) Electrocatalysis Superoxide dismutase Electrochemistry Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4325 , http://hdl.handle.net/10962/d1004985
- Description: Syntheses, spectral, electrochemical, and spectroelectrochemical studies of iron, cobalt, and manganese phthalocyanines are reported. The novel coordination of cobalt tetracarboxy metallophthalocyanine to an electrode premodified with aryl radicals and its use in the detection of thiocyanate are reported. This work describes the catalytic activity of cobalt phthalocyanine (CoPc) derivatives adsorbed onto glassy carbon electrodes for the electrocatalytical detection of nitrite, Lcysteine, and melatonin. The modified electrodes efficiently detected nitrite. The CoPc derivative modified electrodes proficiently detected L-cysteine whereas an un-modified electrode could not. This work presents the innovative electrochemical detection of melatonin using electrodes adsorbed with CoPc derivatives. These electrodes detected melatonin at more favorable electrochemical parameters relative to an un-modified gold electrode. The limits of melatonin detection of the modified electrodes lay in the 10⁻⁷ to 10⁻⁶ M region. The modified electrodes accurately detected capsule melatonin concentrations as specified by the supplier and could differentiate between a mixture of melatonin, tryptophan, and ascorbic acid. They reliably detected nitrite, L-cysteine, and melatonin in the 10⁻⁴ to 10⁻² M region. Metallophthalocyanine complexes substituted with thio groups were employed as self assembled monolayers (SAMs). Voltammetry, impedance, atomic force microscopy, and scanning electrochemical microscopy proved that the SAMs all act as selective and efficient barriers to ion permeability. All the SAMs in this work can be used as effective electrochemical sensors of nitrite and L-cysteine in the 10⁻⁴ to 10⁻² M region with competitive limits of detection whereas an un-modified electrode cannot detect Lcysteine. The manganese phthalocyanine SAM modified electrodes are arguably better nitrite and L-cysteine electrocatalysts relative to their iron and cobalt counterparts. Manganese phthalocyanines were used as superoxide dismutase (SOD) mimics. All manganese phthalocyanine complexes in this work acted as SOD mimics in an enzymatic system of superoxide production. From cellular studies, complexes 6d, 6e, 8d, 8e act as intracellular SOD mimics and are without significantly high cellular toxicity.
- Full Text:
- Date Issued: 2010
Photophysiochemical studies of d¹⁰ metallophthalocyanines and their interaction with nanoparticles
- Chidawanyika, Wadzanai Janet Upenyu
- Authors: Chidawanyika, Wadzanai Janet Upenyu
- Date: 2010
- Subjects: Nanoparticles Phthalocyanines Photochemistry Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4335 , http://hdl.handle.net/10962/d1004996
- Description: The syntheses, extensive spectroscopic characterization, photophysical and photochemical studies have been conducted for a variation of d10 metallophthaloycanines (MPcs). Comparisons have been made taking into consideration the nfluence of the central metal ion, solvent properties, substituent type and position. Coordination to heavy central metals i.e. Hg gives enhanced triplet state properties. Low symmetry metallophthalocyanine complexes were similarly haracterized and the influence of nteractions with nanoparticles on their photophysical and photochemical properties determined. The MPcs have been linked and adsorbed or mixed with nanoparticles i.e. hemically functionalized single-walled carbon nanotubes SWCNT) and mercaptocarboxylic acid capped CdTe quantum dots (QDs) and changes in the spectra accounted for with respect to the proposed conjugate structures. Distinct differences ccur for linked and adsorbed or mixed conjugates in the bsorption, infrared (IR) and Raman spectra and for thermal ravimetric decay profiles, suggesting successful formation f covalent bonds (linked) and point to structurally ifferent materials. SWCNT quench MPc fluorescence by a photoinduced electron transfer mediated process to give low fluorescence quantum yields. The QDs were used as energy transfer donors and facilitate energy transfer, through Förster resonance energy transfer (FRET) from the QDs to the MPcs. Improved FRET efficiencies were found for linked MPc-QD conjugates relative to the mixed species. Photophysicochemical properties of MPcs were, in general, improved as a result of interactions with nanoparticles.
- Full Text:
- Date Issued: 2010
- Authors: Chidawanyika, Wadzanai Janet Upenyu
- Date: 2010
- Subjects: Nanoparticles Phthalocyanines Photochemistry Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4335 , http://hdl.handle.net/10962/d1004996
- Description: The syntheses, extensive spectroscopic characterization, photophysical and photochemical studies have been conducted for a variation of d10 metallophthaloycanines (MPcs). Comparisons have been made taking into consideration the nfluence of the central metal ion, solvent properties, substituent type and position. Coordination to heavy central metals i.e. Hg gives enhanced triplet state properties. Low symmetry metallophthalocyanine complexes were similarly haracterized and the influence of nteractions with nanoparticles on their photophysical and photochemical properties determined. The MPcs have been linked and adsorbed or mixed with nanoparticles i.e. hemically functionalized single-walled carbon nanotubes SWCNT) and mercaptocarboxylic acid capped CdTe quantum dots (QDs) and changes in the spectra accounted for with respect to the proposed conjugate structures. Distinct differences ccur for linked and adsorbed or mixed conjugates in the bsorption, infrared (IR) and Raman spectra and for thermal ravimetric decay profiles, suggesting successful formation f covalent bonds (linked) and point to structurally ifferent materials. SWCNT quench MPc fluorescence by a photoinduced electron transfer mediated process to give low fluorescence quantum yields. The QDs were used as energy transfer donors and facilitate energy transfer, through Förster resonance energy transfer (FRET) from the QDs to the MPcs. Improved FRET efficiencies were found for linked MPc-QD conjugates relative to the mixed species. Photophysicochemical properties of MPcs were, in general, improved as a result of interactions with nanoparticles.
- Full Text:
- Date Issued: 2010
Natural enemies from South Africa for biological control of Lagarosiphon major (Ridl.) Moss ex Wager (Hydrocharitaceae) in Europe
- Baars, Jan-Robert, Coetzee, Julie A, Martin, Grant D, Hill, Martin P, Caffrey, J M
- Authors: Baars, Jan-Robert , Coetzee, Julie A , Martin, Grant D , Hill, Martin P , Caffrey, J M
- Date: 2010
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76914 , vital:30637 , https://doi.org/10.1007/s10750-010-0427-0
- Description: The non-native invasive plant, Lagarosiphon major (Hydrocharitaceae) is a submersed aquatic macrophyte that poses a significant threat to water bodies in Europe. Dense infestations prove difficult to manage using traditional methods. In order to initiate a biocontrol programme, a survey for natural enemies of Lagarosiphon was conducted in South Africa. Several phytophagous species were recorded for the first time, with at least three showing notable promise as candidate agents. Amongst these, a leaf-mining fly, Hydrellia sp. (Ephydridae) that occurred over a wide distribution causes significant leaf damage despite high levels of parasitism by braconid wasps. Another yet unidentified fly was recorded mining the stem of L. major. Two leaf-feeding and shoot boring weevils, cf. Bagous sp. (Curculionidae) were recorded damaging the shoot tips and stunting the growth of the stem. Several leaf-feeding lepidopteran species (Nymphulinae) were frequently recorded, but are expected to feed on a wide range of plant species and are not considered for importation before other candidates are assessed. The discovery of several natural enemies in the country of origin improves the biological control prospects of L. major in Europe.
- Full Text:
- Date Issued: 2010
- Authors: Baars, Jan-Robert , Coetzee, Julie A , Martin, Grant D , Hill, Martin P , Caffrey, J M
- Date: 2010
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76914 , vital:30637 , https://doi.org/10.1007/s10750-010-0427-0
- Description: The non-native invasive plant, Lagarosiphon major (Hydrocharitaceae) is a submersed aquatic macrophyte that poses a significant threat to water bodies in Europe. Dense infestations prove difficult to manage using traditional methods. In order to initiate a biocontrol programme, a survey for natural enemies of Lagarosiphon was conducted in South Africa. Several phytophagous species were recorded for the first time, with at least three showing notable promise as candidate agents. Amongst these, a leaf-mining fly, Hydrellia sp. (Ephydridae) that occurred over a wide distribution causes significant leaf damage despite high levels of parasitism by braconid wasps. Another yet unidentified fly was recorded mining the stem of L. major. Two leaf-feeding and shoot boring weevils, cf. Bagous sp. (Curculionidae) were recorded damaging the shoot tips and stunting the growth of the stem. Several leaf-feeding lepidopteran species (Nymphulinae) were frequently recorded, but are expected to feed on a wide range of plant species and are not considered for importation before other candidates are assessed. The discovery of several natural enemies in the country of origin improves the biological control prospects of L. major in Europe.
- Full Text:
- Date Issued: 2010
Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes
- Mashazi, Philani N, Nyokong, Tebello
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
A bioinorganic investigation of some metal complexes of the Schiff base, N,N'-bis(3-methoxysalicylaldimine)propan-2-ol
- Authors: Mopp, Estelle
- Date: 2010 , 2012-04-13
- Subjects: Schiff bases , Bioinorganic chemistry , Metal complexes , Transition metal complexes , Transition metals , Cancer -- Chemotherapy , Ligands -- Toxicity , Antineoplastic agents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4413 , http://hdl.handle.net/10962/d1006768 , Schiff bases , Bioinorganic chemistry , Metal complexes , Transition metal complexes , Transition metals , Cancer -- Chemotherapy , Ligands -- Toxicity , Antineoplastic agents
- Description: This thesis includes the synthesis, characterisation, antioxidant and antimicrobial activities of Cu(II)-, Co(II)- and Co(III) complexes with N,N'-bis(3- methoxysalicylaldimine)propan-2-ol, 2-OH-oVANPN. The Schiff base ligand, 2-OHoVANPN, is derived from o-vanillin and 1,3-diaminopropan-2-ol. The o-vanillin condensed with 1,3-diaminopropan-2-ol in a 2:1 molar ratio yields this potential tetraor pentadentate ligand. The complexes synthesized are tetra (or penta or hexa) coordinated. Formation of the complexes is symbolized as follows:- MX₂ + 2-OH-oVANPN (2:1) -> [M(2-OH-oVANPN)Xn] + HnX MX₂ + 2-OH-oVANPN (2:1) -> [Mn(2-OH-oVANPN)OH] + H₂X₂ MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M(1:1)X₂] MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M₃(1:1)X₄] M = Cu(II), Co(II) or Co(III); X = Cl; n = 1, 2. Their structural features have been deduced from their elemental analytical data, IR spectral data, and electronic spectral data. With the exception of {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆}(A4), the Cu(II) complexes were monomeric with 2-OH-oVANPN acting as a tetradentate ligand. A binuclear Co(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), was synthesised and the rest of the Co(II) and Co(III) complexes were monomeric with chloride ions coordinating to the metal centre in some cases. Electronic data suggest that the cobalt(II) complexes have octahedral geometries and the copper(II) complexes have square planar structures – Co(III) is likely to be octahedral. Thermal analyses, which included the copper-block-method for determining sublimation temperatures, revealed that some copper(II) and cobalt(II) complexes are hygroscopic and sublime at 200 °C and below. DSC analyses of the Cu(II) complexes gave exotherms around 300 °C for complexes K[Cu(C₁₉H₂₀N₂O₅)(OH)]·2H₂O (A1) and [Cu(C₁₁H15N₂O₃)(Cl)₂]·2H₂O (A2) and above 400 °C for [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3) and {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4). Antioxidant studies were carried out against the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·). The cobalt(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), which was synthesized in the presence of KOH, had no antioxidant activity, whilst the other cobalt(II) complexes, [Co(C₁₇H₁₇N₂O₅(Cl))]·1½H₂O (B2), [Co(C₁₉H₂₂N₂O₅) (Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B4), which were synthesised in the absence of KOH, demonstrated antioxidant activity. The latter complexes are candidates for cancer cell line testing, while [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3), {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4), [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) may show anticancer activity through possible hydrolysis products. Most of the complexes synthesized displayed antimicrobial activity against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Aspergillus niger and Candida albicans. The results indicated that complexes [Cu(C₁₁H₁₆N₂O₃)(Cl)₂](A3), [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) are active against the Gram-negative Ps. aeruginosa and that the ligand, 2-OH-oVANPN, did not have any activity. The same trend was observed with 2-OH-oVANPN, {Cu₃(C₁₁H₁₄N₂O₃)(Cl)4(H₂O)₆} (A4) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) against the Gram-positive S. aureus. As for activity against E. coli and C. albicans, some complexes showed more activity than the ligand. There is an observed trend here that the metal complexes are more active (toxic) than the corresponding ligand, which is in agreement with Tweedy’s chelation theory.
- Full Text:
- Date Issued: 2010
- Authors: Mopp, Estelle
- Date: 2010 , 2012-04-13
- Subjects: Schiff bases , Bioinorganic chemistry , Metal complexes , Transition metal complexes , Transition metals , Cancer -- Chemotherapy , Ligands -- Toxicity , Antineoplastic agents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4413 , http://hdl.handle.net/10962/d1006768 , Schiff bases , Bioinorganic chemistry , Metal complexes , Transition metal complexes , Transition metals , Cancer -- Chemotherapy , Ligands -- Toxicity , Antineoplastic agents
- Description: This thesis includes the synthesis, characterisation, antioxidant and antimicrobial activities of Cu(II)-, Co(II)- and Co(III) complexes with N,N'-bis(3- methoxysalicylaldimine)propan-2-ol, 2-OH-oVANPN. The Schiff base ligand, 2-OHoVANPN, is derived from o-vanillin and 1,3-diaminopropan-2-ol. The o-vanillin condensed with 1,3-diaminopropan-2-ol in a 2:1 molar ratio yields this potential tetraor pentadentate ligand. The complexes synthesized are tetra (or penta or hexa) coordinated. Formation of the complexes is symbolized as follows:- MX₂ + 2-OH-oVANPN (2:1) -> [M(2-OH-oVANPN)Xn] + HnX MX₂ + 2-OH-oVANPN (2:1) -> [Mn(2-OH-oVANPN)OH] + H₂X₂ MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M(1:1)X₂] MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M₃(1:1)X₄] M = Cu(II), Co(II) or Co(III); X = Cl; n = 1, 2. Their structural features have been deduced from their elemental analytical data, IR spectral data, and electronic spectral data. With the exception of {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆}(A4), the Cu(II) complexes were monomeric with 2-OH-oVANPN acting as a tetradentate ligand. A binuclear Co(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), was synthesised and the rest of the Co(II) and Co(III) complexes were monomeric with chloride ions coordinating to the metal centre in some cases. Electronic data suggest that the cobalt(II) complexes have octahedral geometries and the copper(II) complexes have square planar structures – Co(III) is likely to be octahedral. Thermal analyses, which included the copper-block-method for determining sublimation temperatures, revealed that some copper(II) and cobalt(II) complexes are hygroscopic and sublime at 200 °C and below. DSC analyses of the Cu(II) complexes gave exotherms around 300 °C for complexes K[Cu(C₁₉H₂₀N₂O₅)(OH)]·2H₂O (A1) and [Cu(C₁₁H15N₂O₃)(Cl)₂]·2H₂O (A2) and above 400 °C for [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3) and {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4). Antioxidant studies were carried out against the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·). The cobalt(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), which was synthesized in the presence of KOH, had no antioxidant activity, whilst the other cobalt(II) complexes, [Co(C₁₇H₁₇N₂O₅(Cl))]·1½H₂O (B2), [Co(C₁₉H₂₂N₂O₅) (Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B4), which were synthesised in the absence of KOH, demonstrated antioxidant activity. The latter complexes are candidates for cancer cell line testing, while [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3), {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4), [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) may show anticancer activity through possible hydrolysis products. Most of the complexes synthesized displayed antimicrobial activity against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Aspergillus niger and Candida albicans. The results indicated that complexes [Cu(C₁₁H₁₆N₂O₃)(Cl)₂](A3), [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) are active against the Gram-negative Ps. aeruginosa and that the ligand, 2-OH-oVANPN, did not have any activity. The same trend was observed with 2-OH-oVANPN, {Cu₃(C₁₁H₁₄N₂O₃)(Cl)4(H₂O)₆} (A4) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) against the Gram-positive S. aureus. As for activity against E. coli and C. albicans, some complexes showed more activity than the ligand. There is an observed trend here that the metal complexes are more active (toxic) than the corresponding ligand, which is in agreement with Tweedy’s chelation theory.
- Full Text:
- Date Issued: 2010
Microbial ecology of the Buffalo River in response to water quality changes
- Authors: Zuma, Bongumusa Msizi
- Date: 2010
- Subjects: Water quality -- South Africa -- Buffalo River (Eastern Cape) , Microbial ecology -- South Africa -- Buffalo River (Eastern Cape) , River Health Programme (South Africa)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:6038 , http://hdl.handle.net/10962/d1006182 , Water quality -- South Africa -- Buffalo River (Eastern Cape) , Microbial ecology -- South Africa -- Buffalo River (Eastern Cape) , River Health Programme (South Africa)
- Description: South Africa’s freshwater quality and quantity is declining and consequently impacting on the ecological health of these ecosystems, due to increased agricultural, urban and industrial developments. The River Health Programme (RHP) was designed for monitoring and assessing the ecological health of freshwater ecosystems in South Africa, in order to effectively manage these aquatic resources. The RHP utilises biological indicators such as in-stream biota as a structured and sensitive tool for assessing ecosystem health. Although the RHP has been widely implemented across South Africa, no attempts have been made to explore microbial ecology as a tool that could be included as one of the RHP indices. This study used selected microbial responses and water physico-chemical parameters to assess the current water quality status of the Buffalo River. This study showed that water quality impairments compounded in the urban regions of King William’s Town and Zwelitsha and also downstream of the Bridle Drift Dam. The results also showed that the lower and the upper catchments of the Buffalo River were not significantly different in terms of water physico-chemistry and microbiology, as indicated by low stress levels of an NMDS plot. Though similarities were recorded between impacted and reference sites, the results strongly showed that known impacted sites recorded the poorest water physico-chemistry, including the Yellowwoods River. However, the Laing Dam provided a buffer effect on contributions of the Yellowwoods River into the Buffalo River. Multivariate analysis showed that microbial cell counts were not influenced by water physico-chemical changes, whilst microbial activity from the water and biofilm habitats showed significant correlation levels to water physico-chemical changes. This study demonstrated that further investigations towards exploitation of microbial activity responses to water physico-chemical quality changes should be channelled towards the development of microbiological assessment index for inclusion in the RHP.
- Full Text:
- Date Issued: 2010
- Authors: Zuma, Bongumusa Msizi
- Date: 2010
- Subjects: Water quality -- South Africa -- Buffalo River (Eastern Cape) , Microbial ecology -- South Africa -- Buffalo River (Eastern Cape) , River Health Programme (South Africa)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:6038 , http://hdl.handle.net/10962/d1006182 , Water quality -- South Africa -- Buffalo River (Eastern Cape) , Microbial ecology -- South Africa -- Buffalo River (Eastern Cape) , River Health Programme (South Africa)
- Description: South Africa’s freshwater quality and quantity is declining and consequently impacting on the ecological health of these ecosystems, due to increased agricultural, urban and industrial developments. The River Health Programme (RHP) was designed for monitoring and assessing the ecological health of freshwater ecosystems in South Africa, in order to effectively manage these aquatic resources. The RHP utilises biological indicators such as in-stream biota as a structured and sensitive tool for assessing ecosystem health. Although the RHP has been widely implemented across South Africa, no attempts have been made to explore microbial ecology as a tool that could be included as one of the RHP indices. This study used selected microbial responses and water physico-chemical parameters to assess the current water quality status of the Buffalo River. This study showed that water quality impairments compounded in the urban regions of King William’s Town and Zwelitsha and also downstream of the Bridle Drift Dam. The results also showed that the lower and the upper catchments of the Buffalo River were not significantly different in terms of water physico-chemistry and microbiology, as indicated by low stress levels of an NMDS plot. Though similarities were recorded between impacted and reference sites, the results strongly showed that known impacted sites recorded the poorest water physico-chemistry, including the Yellowwoods River. However, the Laing Dam provided a buffer effect on contributions of the Yellowwoods River into the Buffalo River. Multivariate analysis showed that microbial cell counts were not influenced by water physico-chemical changes, whilst microbial activity from the water and biofilm habitats showed significant correlation levels to water physico-chemical changes. This study demonstrated that further investigations towards exploitation of microbial activity responses to water physico-chemical quality changes should be channelled towards the development of microbiological assessment index for inclusion in the RHP.
- Full Text:
- Date Issued: 2010
Isolation and evolution of novel nucleoside phosphorylases
- Authors: Visser, Daniel Finsch
- Date: 2010
- Subjects: AIDS (Disease) -- Treatment -- Africa HIV Infections -- Treatment -- Africa AIDS (Disease) -- Patients -- Africa HIV-Positive persons -- Africa Antiretroviral agents Pyrimidine nucleotides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3972 , http://hdl.handle.net/10962/d1004031
- Description: Approximately 33.4 million people are living with HIV/AIDS. Of those, 97% live in low and middle income countries, with 22.4 million in sub-Saharan Africa. Only 42% of the people who require anti-retrovirals (ARVs) in low to middle income countries are receiving anti-retroviral therapy (ART). There is a need to develop novel and cost effective methods for producing antiretroviral drugs. Stavudine and azidothymidine (AZT) were identified as potential targets because they could both be produced through a common intermediate – 5 methyluridine (5-MU). It has been established that the biocatalytic production of 5-methyluridine is possible through a reaction known as transglycosylation, in a process which has not previously been demonstrated as commercially viable. A selection of biocatalysts were expressed either in recombinant E. coli strains or in the wild type organisms, purified and then screened for their ability to produce 5-MU. A combination of Bacillus halodurans purine nucleoside phosphorylase 1 (BHPNP1) and E. coli uridine phosphorylase (EcUP) gave the highest 5-MU yield (80%). This result represents the first combination of free enzymes from different organisms, giving high yields of 5-MU under high substrate conditions. Both enzymes were purified and successfully characterised. The established pH optimum was pH 7.0 for both enzymes. Temperature optima and stability data for BHPNP1 (70 C and t1/2 at 60 C of 20.8 h) indicated that the biocatalytic step was operating within the capabilities of this enzyme and would operate well at elevated temperatures (up to 60 C). Conversely, the temperature optimum and stability data for EcUP (optimum of 40 C and t1/2 at 60 C of 9.9 h) indicated that the enzyme remained active at 40 C for the duration of a 25 h biotransformation, but at 60 C would only be operating at 20% of its optimum activity and would lose activity rapidly. BHPNP1 and EcUP were used in a bench scale (650 ml) transglycosylation for the production of 5-MU. A 5-MU yield of 79.1% was obtained at this scale with a reactor productivity of 1.37 g.l-1.h-1. Iterative saturation mutagenesis was used to rapidly evolve EcUP for improved thermostability. A moderately high throughput colorimetric method was developed for screening the mutants based on the release of p-nitrophenol upon phosphorolysis of a pyrimidine nucleoside analogue. By screening under 20 000 clones the mutant UPL8 was isolated. The mutant enzyme showed an optimum temperature of 60 C and improved stability at 60 C (t1/2 = 17.3 h). The increase in stability of UPL8 is due to only 2 mutations (Lys235Arg, Gln236Ala). These mutations may have caused an increase in stability due to interactions with other structural units in the protein, stabilization of the entrance to the binding pocket, or by decreasing the flexibility of the α-helix at the N-terminus. Transglycosylation experiments showed that the mutant enzyme UPL8 is a superior catalyst for the production of 5-MU. A 300% increase in reactor productivity was noted when free enzyme preparations of UPL8 was combined with BHPNP1 at 1.5% m.m-1 substrate loading. The high yield of 5-MU (75-80% mol.mol-1) was maintained at 9% m.m-1 substrate loading. A commercially viable productivity of 31 g.l-1.h-1 was thus realised. Further optimisation of the process could produce still higher productivities. Future work in directed evolution of nucleoside phosphorylases is envisaged for improved stability and enhanced substrate range for application to other commercially relevant transglycosylation reactions.
- Full Text:
- Date Issued: 2010
- Authors: Visser, Daniel Finsch
- Date: 2010
- Subjects: AIDS (Disease) -- Treatment -- Africa HIV Infections -- Treatment -- Africa AIDS (Disease) -- Patients -- Africa HIV-Positive persons -- Africa Antiretroviral agents Pyrimidine nucleotides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3972 , http://hdl.handle.net/10962/d1004031
- Description: Approximately 33.4 million people are living with HIV/AIDS. Of those, 97% live in low and middle income countries, with 22.4 million in sub-Saharan Africa. Only 42% of the people who require anti-retrovirals (ARVs) in low to middle income countries are receiving anti-retroviral therapy (ART). There is a need to develop novel and cost effective methods for producing antiretroviral drugs. Stavudine and azidothymidine (AZT) were identified as potential targets because they could both be produced through a common intermediate – 5 methyluridine (5-MU). It has been established that the biocatalytic production of 5-methyluridine is possible through a reaction known as transglycosylation, in a process which has not previously been demonstrated as commercially viable. A selection of biocatalysts were expressed either in recombinant E. coli strains or in the wild type organisms, purified and then screened for their ability to produce 5-MU. A combination of Bacillus halodurans purine nucleoside phosphorylase 1 (BHPNP1) and E. coli uridine phosphorylase (EcUP) gave the highest 5-MU yield (80%). This result represents the first combination of free enzymes from different organisms, giving high yields of 5-MU under high substrate conditions. Both enzymes were purified and successfully characterised. The established pH optimum was pH 7.0 for both enzymes. Temperature optima and stability data for BHPNP1 (70 C and t1/2 at 60 C of 20.8 h) indicated that the biocatalytic step was operating within the capabilities of this enzyme and would operate well at elevated temperatures (up to 60 C). Conversely, the temperature optimum and stability data for EcUP (optimum of 40 C and t1/2 at 60 C of 9.9 h) indicated that the enzyme remained active at 40 C for the duration of a 25 h biotransformation, but at 60 C would only be operating at 20% of its optimum activity and would lose activity rapidly. BHPNP1 and EcUP were used in a bench scale (650 ml) transglycosylation for the production of 5-MU. A 5-MU yield of 79.1% was obtained at this scale with a reactor productivity of 1.37 g.l-1.h-1. Iterative saturation mutagenesis was used to rapidly evolve EcUP for improved thermostability. A moderately high throughput colorimetric method was developed for screening the mutants based on the release of p-nitrophenol upon phosphorolysis of a pyrimidine nucleoside analogue. By screening under 20 000 clones the mutant UPL8 was isolated. The mutant enzyme showed an optimum temperature of 60 C and improved stability at 60 C (t1/2 = 17.3 h). The increase in stability of UPL8 is due to only 2 mutations (Lys235Arg, Gln236Ala). These mutations may have caused an increase in stability due to interactions with other structural units in the protein, stabilization of the entrance to the binding pocket, or by decreasing the flexibility of the α-helix at the N-terminus. Transglycosylation experiments showed that the mutant enzyme UPL8 is a superior catalyst for the production of 5-MU. A 300% increase in reactor productivity was noted when free enzyme preparations of UPL8 was combined with BHPNP1 at 1.5% m.m-1 substrate loading. The high yield of 5-MU (75-80% mol.mol-1) was maintained at 9% m.m-1 substrate loading. A commercially viable productivity of 31 g.l-1.h-1 was thus realised. Further optimisation of the process could produce still higher productivities. Future work in directed evolution of nucleoside phosphorylases is envisaged for improved stability and enhanced substrate range for application to other commercially relevant transglycosylation reactions.
- Full Text:
- Date Issued: 2010
Photophysical properties of newly synthesized fluorinated zinc phthalocyanines in the presence of CdTe quantum dots and the accompanying energy transfer processes
- Erdoğmuş, Ali, Moeno, Sharon, Litwinski, Christian, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Moeno, Sharon , Litwinski, Christian , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262671 , vital:53543 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.014"
- Description: The photophysical properties of two newly synthesized phthalocyanines (Pcs) were studied in the presence and the absence of 3-mercaptopropionic acid (MPA) capped quantum dots (QDs). Energy transfer processes resulting from the combination of QDs and the Pcs: 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyaninato)zinc(II) (TtfmMPyZnPc, 3) and 4-(tetrakis-5-(trifluoromethyl)-2-pyridyloxyphthalocyaninato) zinc(II) (TtfmPyZnPc, 4) were also studied. The photophysical properties of the Pcs in the presence of QDs were enhanced and Förster resonance energy transfer (FRET) was observed with the phthalocyanines used. The efficiency of FRET between the QDs and TtfmMPyZnPc and TtfmPyZnPc was found to be 0.31% and 0.45% in DMSO and 0.24% and 0.32% in pyridine, respectively. The triplet state quantum yields for TtfmMPyZnPc and TtfmPyZnPc were found to be 0.86 and 0.74 in DMSO and 0.83 and 0.76 in pyridine.
- Full Text:
- Date Issued: 2010
- Authors: Erdoğmuş, Ali , Moeno, Sharon , Litwinski, Christian , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262671 , vital:53543 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.014"
- Description: The photophysical properties of two newly synthesized phthalocyanines (Pcs) were studied in the presence and the absence of 3-mercaptopropionic acid (MPA) capped quantum dots (QDs). Energy transfer processes resulting from the combination of QDs and the Pcs: 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyaninato)zinc(II) (TtfmMPyZnPc, 3) and 4-(tetrakis-5-(trifluoromethyl)-2-pyridyloxyphthalocyaninato) zinc(II) (TtfmPyZnPc, 4) were also studied. The photophysical properties of the Pcs in the presence of QDs were enhanced and Förster resonance energy transfer (FRET) was observed with the phthalocyanines used. The efficiency of FRET between the QDs and TtfmMPyZnPc and TtfmPyZnPc was found to be 0.31% and 0.45% in DMSO and 0.24% and 0.32% in pyridine, respectively. The triplet state quantum yields for TtfmMPyZnPc and TtfmPyZnPc were found to be 0.86 and 0.74 in DMSO and 0.83 and 0.76 in pyridine.
- Full Text:
- Date Issued: 2010