The coordination chemistry of Rhenium(V) with multidentate no-donor ligands
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
Lead-radium dating of two deep-water fishes from the southern hemisphere, Patagonian toothfish (Dissostichus eleginoides) and Orange Roughy (Hoplostethus atlanticus)
- Authors: Andrews, Allen Hia
- Date: 2009
- Subjects: Fishes -- Age determination , Fishes -- Southern hemisphere -- Longevity , Fishes -- Growth , Radioactive dating , Patagonian toothfish , Patagonian toothfish -- Fisheries , Orange roughy , Orange roughy -- Fisheries , Deep-sea fishes -- Southern hemisphere , Deep-sea fisheries , Deep-sea fisheries -- Southern hemisphere
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5295 , http://hdl.handle.net/10962/d1005140
- Description: Patagonian toothfish (Dissostichus eleginoides) or "Chilean sea bass" support a valuable and controversial fishery, but the life history is little known and longevity estimates range from ~20 to more than 40 or 50 yr. In this study, lead-radium dating provided validated age estimates from juveniles to older adults, supporting the use of otoliths as accurate indicators of age. The oldest age groups were near 30 yr, which provided support for age estimates exceeding 40 or 50 yr from grow zone counts in otolith sections. Hence, scale reading, which rarely exceeds 20 years, has the potential for age underestimation. Lead-radium dating revealed what may be minor differences in age interpretation between two facilities and findings may provide an age-validated opportunity for the CCAMLR Otolith Network to reassess otolith interpretations. Orange roughy (Hoplostethus atlanticus) support a major deep-sea fishery and stock assessments often depend on age analyses, but lifespan estimates range from ~20 to over 100 yr and validation of growth zone counts remained unresolved. An early application of lead-radium dating supported centenarian ages, but the findings were met with disbelief and some studies have attempted to discredit the technique and the long lifespan. In this study, an improved lead-radium dating technique used smaller samples than previously possible and circumvented assumptions that were previously necessary. Lead-radium dating of otolith cores, the first few years of growth, provided ratios that correlated well with the ingrowth curve. This provided robust support for age estimates from otolith thin sections. Use of radiometric ages as independent age estimates indicated the fish in the oldest group were at least 93 yr. Lead-radium dating has validated a centenarian lifespan for orange roughy. To date, radium-226 has been measured in otoliths of 39 fish species ranging from the northern Pacific and Atlantic Oceans to the Southern Ocean. In total, 367 reliable radium-226 measurements were made in 36 studies since the first lead-radium dating study on fish in 1982. The activity of radium-226 measurements ranged over 3 orders of magnitude (<0.001 to >1.0 dpm.g⁻¹). An analysis revealed ontogenetic differences in radium-226 uptake that may be attributed to changes in habitat or diet. Radiometric age from otolith core studies was used to describe a radium-226 uptake time-series for some species, which revealed interesting patterns over long periods. This synopsis provides information on the uptake of radium-226 to otoliths from an environmental perspective, which can be used as a basis for future studies.
- Full Text:
- Date Issued: 2009
- Authors: Andrews, Allen Hia
- Date: 2009
- Subjects: Fishes -- Age determination , Fishes -- Southern hemisphere -- Longevity , Fishes -- Growth , Radioactive dating , Patagonian toothfish , Patagonian toothfish -- Fisheries , Orange roughy , Orange roughy -- Fisheries , Deep-sea fishes -- Southern hemisphere , Deep-sea fisheries , Deep-sea fisheries -- Southern hemisphere
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5295 , http://hdl.handle.net/10962/d1005140
- Description: Patagonian toothfish (Dissostichus eleginoides) or "Chilean sea bass" support a valuable and controversial fishery, but the life history is little known and longevity estimates range from ~20 to more than 40 or 50 yr. In this study, lead-radium dating provided validated age estimates from juveniles to older adults, supporting the use of otoliths as accurate indicators of age. The oldest age groups were near 30 yr, which provided support for age estimates exceeding 40 or 50 yr from grow zone counts in otolith sections. Hence, scale reading, which rarely exceeds 20 years, has the potential for age underestimation. Lead-radium dating revealed what may be minor differences in age interpretation between two facilities and findings may provide an age-validated opportunity for the CCAMLR Otolith Network to reassess otolith interpretations. Orange roughy (Hoplostethus atlanticus) support a major deep-sea fishery and stock assessments often depend on age analyses, but lifespan estimates range from ~20 to over 100 yr and validation of growth zone counts remained unresolved. An early application of lead-radium dating supported centenarian ages, but the findings were met with disbelief and some studies have attempted to discredit the technique and the long lifespan. In this study, an improved lead-radium dating technique used smaller samples than previously possible and circumvented assumptions that were previously necessary. Lead-radium dating of otolith cores, the first few years of growth, provided ratios that correlated well with the ingrowth curve. This provided robust support for age estimates from otolith thin sections. Use of radiometric ages as independent age estimates indicated the fish in the oldest group were at least 93 yr. Lead-radium dating has validated a centenarian lifespan for orange roughy. To date, radium-226 has been measured in otoliths of 39 fish species ranging from the northern Pacific and Atlantic Oceans to the Southern Ocean. In total, 367 reliable radium-226 measurements were made in 36 studies since the first lead-radium dating study on fish in 1982. The activity of radium-226 measurements ranged over 3 orders of magnitude (<0.001 to >1.0 dpm.g⁻¹). An analysis revealed ontogenetic differences in radium-226 uptake that may be attributed to changes in habitat or diet. Radiometric age from otolith core studies was used to describe a radium-226 uptake time-series for some species, which revealed interesting patterns over long periods. This synopsis provides information on the uptake of radium-226 to otoliths from an environmental perspective, which can be used as a basis for future studies.
- Full Text:
- Date Issued: 2009
Student's van Hiele levels of geometric thought and conception in plane geometry: a collective case study of Nigeria and South Africa
- Authors: Atebe, Humphrey Uyouyo
- Date: 2009
- Subjects: Geometry -- Study and teaching (Secondary) -- Nigeria -- Case studies Geometry -- Study and teaching (Secondary) -- South Africa -- Case studies Mathematics -- Study and teaching (Secondary) -- Nigeria -- Case studies Mathematics -- Study and teaching (Secondary) -- South Africa -- Case studies
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1777 , http://hdl.handle.net/10962/d1003662
- Description: This study is inspired by and utilises the van Hiele theory of geometric thought levels, currently acclaimed as one of the best frameworks for studying teaching and learning processes in geometry. The study aims both to explore and explicate the van Hiele levels of geometric thinking of a selected group of grade 10, 11 and 12 learners in Nigerian and South African schools. The study further aims to provide a rich and indepth description of the geometry instructional practices that possibly contributed to the levels of geometric conceptualisation exhibited by this cohort of high school learners. This collective case study, presented in two volumes, is oriented within an interpretive research paradigm and characterised by both qualitative and quantitative methods. The sample for the study comprised a total of 144 mathematics learners and 6 mathematics teachers from Nigeria and South Africa. They were selected using both purposive and stratified sampling techniques. In using the van Hiele model to interrogate both learners’ levels of geometric conceptualisation and teaching methods in geometry classrooms, the study employs a qualitative and qunatitative approach to the data-collection process, involving the use of questionnaires (in the form of various pen-and-paper tests, hands-on activity-based tests), interviews and classroom videos. Although the data analysis was done largely through descriptive statistics, the whole process inevitably incorporated elements of inferential statistics (e.g. ANOVA and Tukey HSD post-hoc test) in the quest for indepth analysis and deeper interpretation of the data. Learners were assigned to various van Hiele levels, mainly according to Usiskin’s (1982) forced van Hiele level determination scheme. The whole process of analysing the classroom videos involved a consultative panel of 4 observers and 3 critical readers, using the checklist of van Hiele phase descriptors to guide the analysis process. Concerning learners’ levels of geometric conceptualisation, the results from this study reveal that the most of the learners were not yet ready for the formal deductive study of school geometry, as only 2% and 3% of them were respectively at van Hiele levels 3 and 4, while 47%, 22% and 24% were at levels 0, 1 and 2, respectively. More learners from the Nigerian subsample (53%) were at van Hiele level 0 than learners from the South African subsample (41%) at this level. No learner from the Nigerian subsample was at van Hiele level 4, while 6% of the South African learners were at level 4. In general, learners from the Nigerian subsample had a poorer knowledge of school geometry than their peers from the South African subsample, as learners from the latter subsample obtained significantly higher mean scores in the van Hiele Geometry Test (VHGT) and each of the other tests used in this study. Results relating to gender differences in performance generally favour the male learners in this study. For each of the participating schools, learners’ van Hiele levels (as determined by their scores on the VHGT) strongly correlate with their performance in geometry content tests and mathematics generally. For each of the Nigerian and South African subsamples, for n ≤ 2, learners at van Hiele level n obtained higher means on nearly all the tests administered in this study than their peers at level n–1. This finding provides support for the hierarchical property of the van Hiele levels.
- Full Text:
- Date Issued: 2009
- Authors: Atebe, Humphrey Uyouyo
- Date: 2009
- Subjects: Geometry -- Study and teaching (Secondary) -- Nigeria -- Case studies Geometry -- Study and teaching (Secondary) -- South Africa -- Case studies Mathematics -- Study and teaching (Secondary) -- Nigeria -- Case studies Mathematics -- Study and teaching (Secondary) -- South Africa -- Case studies
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1777 , http://hdl.handle.net/10962/d1003662
- Description: This study is inspired by and utilises the van Hiele theory of geometric thought levels, currently acclaimed as one of the best frameworks for studying teaching and learning processes in geometry. The study aims both to explore and explicate the van Hiele levels of geometric thinking of a selected group of grade 10, 11 and 12 learners in Nigerian and South African schools. The study further aims to provide a rich and indepth description of the geometry instructional practices that possibly contributed to the levels of geometric conceptualisation exhibited by this cohort of high school learners. This collective case study, presented in two volumes, is oriented within an interpretive research paradigm and characterised by both qualitative and quantitative methods. The sample for the study comprised a total of 144 mathematics learners and 6 mathematics teachers from Nigeria and South Africa. They were selected using both purposive and stratified sampling techniques. In using the van Hiele model to interrogate both learners’ levels of geometric conceptualisation and teaching methods in geometry classrooms, the study employs a qualitative and qunatitative approach to the data-collection process, involving the use of questionnaires (in the form of various pen-and-paper tests, hands-on activity-based tests), interviews and classroom videos. Although the data analysis was done largely through descriptive statistics, the whole process inevitably incorporated elements of inferential statistics (e.g. ANOVA and Tukey HSD post-hoc test) in the quest for indepth analysis and deeper interpretation of the data. Learners were assigned to various van Hiele levels, mainly according to Usiskin’s (1982) forced van Hiele level determination scheme. The whole process of analysing the classroom videos involved a consultative panel of 4 observers and 3 critical readers, using the checklist of van Hiele phase descriptors to guide the analysis process. Concerning learners’ levels of geometric conceptualisation, the results from this study reveal that the most of the learners were not yet ready for the formal deductive study of school geometry, as only 2% and 3% of them were respectively at van Hiele levels 3 and 4, while 47%, 22% and 24% were at levels 0, 1 and 2, respectively. More learners from the Nigerian subsample (53%) were at van Hiele level 0 than learners from the South African subsample (41%) at this level. No learner from the Nigerian subsample was at van Hiele level 4, while 6% of the South African learners were at level 4. In general, learners from the Nigerian subsample had a poorer knowledge of school geometry than their peers from the South African subsample, as learners from the latter subsample obtained significantly higher mean scores in the van Hiele Geometry Test (VHGT) and each of the other tests used in this study. Results relating to gender differences in performance generally favour the male learners in this study. For each of the participating schools, learners’ van Hiele levels (as determined by their scores on the VHGT) strongly correlate with their performance in geometry content tests and mathematics generally. For each of the Nigerian and South African subsamples, for n ≤ 2, learners at van Hiele level n obtained higher means on nearly all the tests administered in this study than their peers at level n–1. This finding provides support for the hierarchical property of the van Hiele levels.
- Full Text:
- Date Issued: 2009
Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
Characterisation of the plasmodium falciparum Hsp40 chaperones and their partnerships with Hsp70
- Authors: Botha, Melissa
- Date: 2009
- Subjects: Heat shock proteins Plasmodium falciparum Protein folding Molecular chaperones Malaria
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3938 , http://hdl.handle.net/10962/d1003997
- Description: Central to this research, 40 kDa Heat shock proteins (Hsp40s) are known to partner (or cochaperone) 70 kDa Heat shock proteins (Hsp70s), facilitating the selection and transfer of protein substrate to Hsp70 and the stimulation of the protein folding ability of Hsp70. Members of the diverse Hsp70-Hsp40 protein complement of Plasmodium falciparum have been implicated in the cytoprotection of this malaria parasite, and are thought to facilitate the protein folding, assembly and translocation tasks required by the parasite to commandeer the infected human erythrocyte subsequent to invasion. In particular, the parasite has evolved an expanded and specialised 43- member suite of Hsp40 proteins, 19 of which bear an identifiable export motif for secretion into the infected erythrocyte cytoplasm where they potentially interact with human Hsp70. Although type I Hsp40 proteins are representative of typical regulators of Hsp70 activity, only two of these proteins are apparent in the parasite’s Hsp40 complement. These include a characteristic type I Hsp40 termed PfHsp40, and a larger, atypical type I Hsp40 termed Pfj1. Both Hsp40 proteins are predicted to be parasite-resident and are most likely to facilitate the co-chaperone regulation of the highly abundant and stress-inducible Hsp70 homolog, PfHsp70-I. In this work, the co-chaperone functionality of PfHsp40 and Pfj1 was elucidated using in vivo and in vitro assays. Purified recombinant PfHsp40 was shown to stimulate the ATPase activity of PfHsp70-I in in vitro single turnover and steady state ATPase assays, and co-operate with PfHsp70-I in in vitro aggregation suppression assays. In these in vitro assays, heterologous partnerships could be demonstrated between PfHsp70-I and the human Hsp40, Hsj1a, and human Hsp70 and PfHsp40, suggesting a common mode of Hsp70-Hsp40 interaction in the parasite and host organism. The functionality of the signature Hsp40 domain, the Jdomain, of Pfj1 was demonstrated by its ability to replace the equivalent domain of the A. tumefaciens Hsp40, Agt DnaJ, in interactions with the prokaryotic Hsp70, DnaK, in the thermosensitive dnaJ cbpA E. coli OD259 deletion strain. An H33Q mutation introduced into the invariant and crucial HPD tripeptide motif abrogated the functionality of the J-domain in the in vivo complementation system. These findings provide the first evidence for the conservation of the prototypical mode of J-domain based interaction of Hsp40 with Hsp70 in P. falciparum. Immunofluorescence staining revealed the localisation of PfHsp40 to the parasite cytoplasm, and Pfj1 to the parasite cytoplasm and nucleus in cultured intraerythrocytic stage P. falciparum parasites. PfHsp70-I was also shown to localise to the parasite cytoplasm and nucleus in these stages, consistent with the literature. Overall we propose that PfHsp40 and Pfj1 co-localise with and regulate the chaperone activity of PfHsp70-I in P. falciparum. This is the first study to identify and provide evidence for a functional Hsp70-Hsp40 partnership in P. falciparum, and provides a platform for future studies to elucidate the importance of these chaperone partnerships in the establishment and survival of the parasite in the intraerythrocytic-stages of development.
- Full Text:
- Date Issued: 2009
- Authors: Botha, Melissa
- Date: 2009
- Subjects: Heat shock proteins Plasmodium falciparum Protein folding Molecular chaperones Malaria
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3938 , http://hdl.handle.net/10962/d1003997
- Description: Central to this research, 40 kDa Heat shock proteins (Hsp40s) are known to partner (or cochaperone) 70 kDa Heat shock proteins (Hsp70s), facilitating the selection and transfer of protein substrate to Hsp70 and the stimulation of the protein folding ability of Hsp70. Members of the diverse Hsp70-Hsp40 protein complement of Plasmodium falciparum have been implicated in the cytoprotection of this malaria parasite, and are thought to facilitate the protein folding, assembly and translocation tasks required by the parasite to commandeer the infected human erythrocyte subsequent to invasion. In particular, the parasite has evolved an expanded and specialised 43- member suite of Hsp40 proteins, 19 of which bear an identifiable export motif for secretion into the infected erythrocyte cytoplasm where they potentially interact with human Hsp70. Although type I Hsp40 proteins are representative of typical regulators of Hsp70 activity, only two of these proteins are apparent in the parasite’s Hsp40 complement. These include a characteristic type I Hsp40 termed PfHsp40, and a larger, atypical type I Hsp40 termed Pfj1. Both Hsp40 proteins are predicted to be parasite-resident and are most likely to facilitate the co-chaperone regulation of the highly abundant and stress-inducible Hsp70 homolog, PfHsp70-I. In this work, the co-chaperone functionality of PfHsp40 and Pfj1 was elucidated using in vivo and in vitro assays. Purified recombinant PfHsp40 was shown to stimulate the ATPase activity of PfHsp70-I in in vitro single turnover and steady state ATPase assays, and co-operate with PfHsp70-I in in vitro aggregation suppression assays. In these in vitro assays, heterologous partnerships could be demonstrated between PfHsp70-I and the human Hsp40, Hsj1a, and human Hsp70 and PfHsp40, suggesting a common mode of Hsp70-Hsp40 interaction in the parasite and host organism. The functionality of the signature Hsp40 domain, the Jdomain, of Pfj1 was demonstrated by its ability to replace the equivalent domain of the A. tumefaciens Hsp40, Agt DnaJ, in interactions with the prokaryotic Hsp70, DnaK, in the thermosensitive dnaJ cbpA E. coli OD259 deletion strain. An H33Q mutation introduced into the invariant and crucial HPD tripeptide motif abrogated the functionality of the J-domain in the in vivo complementation system. These findings provide the first evidence for the conservation of the prototypical mode of J-domain based interaction of Hsp40 with Hsp70 in P. falciparum. Immunofluorescence staining revealed the localisation of PfHsp40 to the parasite cytoplasm, and Pfj1 to the parasite cytoplasm and nucleus in cultured intraerythrocytic stage P. falciparum parasites. PfHsp70-I was also shown to localise to the parasite cytoplasm and nucleus in these stages, consistent with the literature. Overall we propose that PfHsp40 and Pfj1 co-localise with and regulate the chaperone activity of PfHsp70-I in P. falciparum. This is the first study to identify and provide evidence for a functional Hsp70-Hsp40 partnership in P. falciparum, and provides a platform for future studies to elucidate the importance of these chaperone partnerships in the establishment and survival of the parasite in the intraerythrocytic-stages of development.
- Full Text:
- Date Issued: 2009
Evaluation of a plant-herbivore system in determining potential efficacy of a candidate biological control agent, cornops aquaticum for water hyacinth, eichhornia crassipes
- Authors: Bownes, Angela
- Date: 2009
- Subjects: Water hyacinth -- Control -- South Africa , Eichhornia crassipedes , Pontederiaceae , Grasshoppers , Biological pest control agents -- South Africa , Weeds -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5687 , http://hdl.handle.net/10962/d1005373
- Description: Water hyacinth, Eichhornia crassipes Mart. Solms-Laubach (Pontederiaceae), a freefloating aquatic macrophyte of Neotropical origin, was introduced into South Africa as an ornamental aquarium plant in the early 1900’s. By the 1970’s it had reached pest proportions in dams and rivers around the country. Due to the sustainability, cost efficiency and low environmental risk associated with biological control, this has been a widely used method in an attempt to reduce infestations to below the threshold where they cause economic and ecological damage. To date, five arthropod and one pathogen biocontrol agents have been introduced for the control of water hyacinth but their impact has been variable. It is believed that their efficacy is hampered by the presence of highly eutrophic systems in South Africa in which plant growth is prolific and the negative effects of herbivory are therefore mitigated. It is for these reasons that new, potentially more damaging biocontrol agents are being considered for release. The water hyacinth grasshopper, Cornops aquaticum Brüner (Orthoptera: Acrididae), which is native to South America and Mexico, was brought into quarantine in Pretoria, South Africa in 1995. Although the grasshopper was identified as one of the most damaging insects associated with water hyacinth in its native range, it has not been considered as a biocontrol agent for water hyacinth anywhere else in the world. After extensive host-range testing which revealed it to be safe for release, a release permit for this candidate agent was issued in 2007. However, host specificity testing is no longer considered to be the only important component of pre-release screening of candidate biocontrol agents. Investigating biological and ecological aspects of the plant-herbivore system that will assist in determination of potential establishment, efficacy and the ability to build up good populations in the recipient environment are some of the important factors. This thesis is a pre-release evaluation of C. aquaticum to determine whether it is sufficiently damaging to water hyacinth to warrant its release. It investigated interactions between the grasshopper and water hyacinth under a range of nutrient conditions found in South African water bodies as well as the impact of the grasshopper on the competitive performance of water hyacinth. Both plant growth rates and the response of water hyacinth to herbivory by the grasshopper were influenced by nutrient availability to the plants. The ability of water hyacinth to compensate for loss of tissue through herbivory was greater under eutrophic nutrient conditions. However, a negative linear relationship was found between grasshopper biomass and water hyacinth performance parameters such as biomass accumulation and leaf production, even under eutrophic conditions. Water hyacinth’s compensatory ability in terms of its potential to mitigate to detrimental effects of insect feeding was dependent on the amount of damage caused by herbivory by the grasshopper. Plant biomass and the competitive ability of water hyacinth in relation to another freefloating aquatic weed species were reduced by C. aquaticum under eutrophic nutrient conditions, in a short space of time. It was also found that grasshopper feeding and characteristics related to their population dynamics such as fecundity and survival were significantly influenced by water nutrient availability and that environmental nutrient availability will influence the control potential of this species should it be released in South Africa. Cornops aquaticum shows promise as a biocontrol agent for water hyacinth but additional factors that were not investigated in this study such as compatibility with the South African climate and the current water hyacinth biocontrol agents need to be combined with these data to make a decision on its release. Possible management options for this species if it is to be introduced into South Africa are discussed.
- Full Text:
- Date Issued: 2009
- Authors: Bownes, Angela
- Date: 2009
- Subjects: Water hyacinth -- Control -- South Africa , Eichhornia crassipedes , Pontederiaceae , Grasshoppers , Biological pest control agents -- South Africa , Weeds -- Biological control -- South Africa , Invasive plants -- Biological control -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5687 , http://hdl.handle.net/10962/d1005373
- Description: Water hyacinth, Eichhornia crassipes Mart. Solms-Laubach (Pontederiaceae), a freefloating aquatic macrophyte of Neotropical origin, was introduced into South Africa as an ornamental aquarium plant in the early 1900’s. By the 1970’s it had reached pest proportions in dams and rivers around the country. Due to the sustainability, cost efficiency and low environmental risk associated with biological control, this has been a widely used method in an attempt to reduce infestations to below the threshold where they cause economic and ecological damage. To date, five arthropod and one pathogen biocontrol agents have been introduced for the control of water hyacinth but their impact has been variable. It is believed that their efficacy is hampered by the presence of highly eutrophic systems in South Africa in which plant growth is prolific and the negative effects of herbivory are therefore mitigated. It is for these reasons that new, potentially more damaging biocontrol agents are being considered for release. The water hyacinth grasshopper, Cornops aquaticum Brüner (Orthoptera: Acrididae), which is native to South America and Mexico, was brought into quarantine in Pretoria, South Africa in 1995. Although the grasshopper was identified as one of the most damaging insects associated with water hyacinth in its native range, it has not been considered as a biocontrol agent for water hyacinth anywhere else in the world. After extensive host-range testing which revealed it to be safe for release, a release permit for this candidate agent was issued in 2007. However, host specificity testing is no longer considered to be the only important component of pre-release screening of candidate biocontrol agents. Investigating biological and ecological aspects of the plant-herbivore system that will assist in determination of potential establishment, efficacy and the ability to build up good populations in the recipient environment are some of the important factors. This thesis is a pre-release evaluation of C. aquaticum to determine whether it is sufficiently damaging to water hyacinth to warrant its release. It investigated interactions between the grasshopper and water hyacinth under a range of nutrient conditions found in South African water bodies as well as the impact of the grasshopper on the competitive performance of water hyacinth. Both plant growth rates and the response of water hyacinth to herbivory by the grasshopper were influenced by nutrient availability to the plants. The ability of water hyacinth to compensate for loss of tissue through herbivory was greater under eutrophic nutrient conditions. However, a negative linear relationship was found between grasshopper biomass and water hyacinth performance parameters such as biomass accumulation and leaf production, even under eutrophic conditions. Water hyacinth’s compensatory ability in terms of its potential to mitigate to detrimental effects of insect feeding was dependent on the amount of damage caused by herbivory by the grasshopper. Plant biomass and the competitive ability of water hyacinth in relation to another freefloating aquatic weed species were reduced by C. aquaticum under eutrophic nutrient conditions, in a short space of time. It was also found that grasshopper feeding and characteristics related to their population dynamics such as fecundity and survival were significantly influenced by water nutrient availability and that environmental nutrient availability will influence the control potential of this species should it be released in South Africa. Cornops aquaticum shows promise as a biocontrol agent for water hyacinth but additional factors that were not investigated in this study such as compatibility with the South African climate and the current water hyacinth biocontrol agents need to be combined with these data to make a decision on its release. Possible management options for this species if it is to be introduced into South Africa are discussed.
- Full Text:
- Date Issued: 2009
The development and evaluation of a programme to promote sensitive pscyhotherapeutic practice with gay men and lesbians
- Authors: Coetzee, Catherine Ann
- Date: 2009
- Subjects: Psychotherapy -- Practice -- South Africa Psychoanalysis and homosexuality -- South Africa Homosexuality -- Social aspects -- South Africa Homosexuality -- Psychological aspects -- South Africa Psychotherapy -- Moral and ethical aspects -- South Africa Psychologists -- Training of -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2952 , http://hdl.handle.net/10962/d1002461
- Description: Clinical psychology’s relevance and future viability depend on its ability to render services that are relevant and sensitive to multicultural and minority issues. Lesbian, gay, bisexual and transgendered people are one such group that professional psychology – both in South Africa and abroad - has identified as having unique treatment needs for which psychologists require specialised knowledge and skills in order to render appropriate treatment. Competence to treat non-heterosexual patients has been framed in terms of a gay affirmative paradigm which has as its basic tenet the recognition that same-gender orientation is not pathological but rather a healthy alternative to heterosexuality. From this perspective being “gay friendly” or “gay accepting” is not enough. To implement a gay affirmative approach in practice, practitioners must have resolved their possible prejudice and heterosexist bias and have the requisite knowledge of concerns unique to lesbian, gay, and bisexual (LGB) individuals to be able to apply their skills in a culturally sensitive manner. Although more American post-graduate psychology programmes are addressing sexual diversity, their failure to produce psychologists who feel competent to treat lesbian/gay or bisexual individuals has highlighted the need to develop effective training strategies based on empirical nvestigation. The dearth of comparable data about local South African psychology training prompted this inquiry which had four broad aims namely, (i) to establish to what extent trainees’ prior training had equipped them with the knowledge, awareness, and skills to approach their work with non-heterosexual patients in a gay affirmative manner, and (ii) to implement and (iii) to evaluate to what extent a brief structured training programme is effective in engaging the trainees; in increasing knowledge, in raising awareness, and in changing specific attitudes and imparting specific skills required for treating lesbian and gay patients.; and (iv) what, if any, recommendations should be made for the future with respect to training of sychologists in this area? The field of sexual orientation research has been expanded to include issues pertaining to bisexual, transgendered and intersexed people, but serious time constraints meant that issues pertaining to these groups could not be addressed in depth. Although the exclusion of these groups is problematic and may be seen as reinforcing their invisibility, it was decided to focus primarily on gay and lesbian issues s an introduction to same-sex orientation. It is envisaged that bisexual and transgender issues would be dealt with in depth in more advanced training. Nine trainee psychologists employed at hospitals in the greater Cape Town area volunteered to participate in the programme which comprised a series of two-hour experiential workshops offered once a week over six weeks. The study employed both quantitative and qualitative data analysis methods. The first stage entailed gathering information to better understand trainees’ existing level of competence. Individual interviews were conducted prior to the course to obtain data about their attitudes and perceptions regarding the need for such specialised training, and how qualified they considered themselves to be to treat LGB patients, and their experience in this regard. For the purpose of the over-all analysis information was also gathered about pertinent personal and social characteristics of the trainees, as well as their contact with lesbian/gay persons. In addition, an attitude survey and the Lesbian, Gay, and Bisexual Counselling Self-efficacy Scale (LGB-CSI) were administered to obtain benchmarks against which change could be measured. The second stage involved the implementation of the educational programme and gathering information about trainees’ responses to its various components. This stage concentrated on discovering how individual trainees reacted to material on lesbian, gay, and bisexual issues and how they used the programme to improve their self-awareness and skills. The results indicate that local psychology training might not address same-gender orientation adequately, thus reinforcing trainees’ belief that sexual orientation is irrelevant, and that their generalist training equips them to work with gay/lesbian/bisexual patients. While the training strengthened existing positive attitudes, it was less effective in changing blatant antigay prejudice. However, both quantitative and qualitative data suggest that the programme increased individuals’ awareness and insight into their previously unrecognised heterosexist biases and created greater understanding of the effects of stigmatisation on sexual minority individuals. In addition, the training increased trainee’s sense of competence to provide affirmative treatment as evidenced by the significant differences between the pre- and post-training mean scores on the Relationship, Knowledge, and Advocacy Scales and between the mid- and post-training means scores on the Assessment and Awareness Scales of the LGB-CSI. Despite the limited generalisability of these findings on account of possible sampling bias, the need and value of such training was confirmed by trainees’ recommendation that this programme should be a mandatory offering in the first year of clinical psychology training.
- Full Text:
- Date Issued: 2009
- Authors: Coetzee, Catherine Ann
- Date: 2009
- Subjects: Psychotherapy -- Practice -- South Africa Psychoanalysis and homosexuality -- South Africa Homosexuality -- Social aspects -- South Africa Homosexuality -- Psychological aspects -- South Africa Psychotherapy -- Moral and ethical aspects -- South Africa Psychologists -- Training of -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2952 , http://hdl.handle.net/10962/d1002461
- Description: Clinical psychology’s relevance and future viability depend on its ability to render services that are relevant and sensitive to multicultural and minority issues. Lesbian, gay, bisexual and transgendered people are one such group that professional psychology – both in South Africa and abroad - has identified as having unique treatment needs for which psychologists require specialised knowledge and skills in order to render appropriate treatment. Competence to treat non-heterosexual patients has been framed in terms of a gay affirmative paradigm which has as its basic tenet the recognition that same-gender orientation is not pathological but rather a healthy alternative to heterosexuality. From this perspective being “gay friendly” or “gay accepting” is not enough. To implement a gay affirmative approach in practice, practitioners must have resolved their possible prejudice and heterosexist bias and have the requisite knowledge of concerns unique to lesbian, gay, and bisexual (LGB) individuals to be able to apply their skills in a culturally sensitive manner. Although more American post-graduate psychology programmes are addressing sexual diversity, their failure to produce psychologists who feel competent to treat lesbian/gay or bisexual individuals has highlighted the need to develop effective training strategies based on empirical nvestigation. The dearth of comparable data about local South African psychology training prompted this inquiry which had four broad aims namely, (i) to establish to what extent trainees’ prior training had equipped them with the knowledge, awareness, and skills to approach their work with non-heterosexual patients in a gay affirmative manner, and (ii) to implement and (iii) to evaluate to what extent a brief structured training programme is effective in engaging the trainees; in increasing knowledge, in raising awareness, and in changing specific attitudes and imparting specific skills required for treating lesbian and gay patients.; and (iv) what, if any, recommendations should be made for the future with respect to training of sychologists in this area? The field of sexual orientation research has been expanded to include issues pertaining to bisexual, transgendered and intersexed people, but serious time constraints meant that issues pertaining to these groups could not be addressed in depth. Although the exclusion of these groups is problematic and may be seen as reinforcing their invisibility, it was decided to focus primarily on gay and lesbian issues s an introduction to same-sex orientation. It is envisaged that bisexual and transgender issues would be dealt with in depth in more advanced training. Nine trainee psychologists employed at hospitals in the greater Cape Town area volunteered to participate in the programme which comprised a series of two-hour experiential workshops offered once a week over six weeks. The study employed both quantitative and qualitative data analysis methods. The first stage entailed gathering information to better understand trainees’ existing level of competence. Individual interviews were conducted prior to the course to obtain data about their attitudes and perceptions regarding the need for such specialised training, and how qualified they considered themselves to be to treat LGB patients, and their experience in this regard. For the purpose of the over-all analysis information was also gathered about pertinent personal and social characteristics of the trainees, as well as their contact with lesbian/gay persons. In addition, an attitude survey and the Lesbian, Gay, and Bisexual Counselling Self-efficacy Scale (LGB-CSI) were administered to obtain benchmarks against which change could be measured. The second stage involved the implementation of the educational programme and gathering information about trainees’ responses to its various components. This stage concentrated on discovering how individual trainees reacted to material on lesbian, gay, and bisexual issues and how they used the programme to improve their self-awareness and skills. The results indicate that local psychology training might not address same-gender orientation adequately, thus reinforcing trainees’ belief that sexual orientation is irrelevant, and that their generalist training equips them to work with gay/lesbian/bisexual patients. While the training strengthened existing positive attitudes, it was less effective in changing blatant antigay prejudice. However, both quantitative and qualitative data suggest that the programme increased individuals’ awareness and insight into their previously unrecognised heterosexist biases and created greater understanding of the effects of stigmatisation on sexual minority individuals. In addition, the training increased trainee’s sense of competence to provide affirmative treatment as evidenced by the significant differences between the pre- and post-training mean scores on the Relationship, Knowledge, and Advocacy Scales and between the mid- and post-training means scores on the Assessment and Awareness Scales of the LGB-CSI. Despite the limited generalisability of these findings on account of possible sampling bias, the need and value of such training was confirmed by trainees’ recommendation that this programme should be a mandatory offering in the first year of clinical psychology training.
- Full Text:
- Date Issued: 2009
An investigation into the use of guidelines and patterns in the interaction design process
- Authors: Cowley, Niel Lester Orr
- Date: 2009
- Subjects: Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10466 , http://hdl.handle.net/10948/1062 , Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Description: Design guidelines are used in interaction design (IxD) for physical design and for evaluating the usability of designs and interactive products. Guidelines are widely used for physical design and evaluation, but have a number of problems. IxD patterns have been proposed as an alternative to guidelines, as they are claimed to have several advantages over guidelines. A small number of empirical studies provide evidence that patterns are beneficial when used in IxD. Additional research on the usefulness of IxD patterns is required. The primary research question investigated in this thesis was thus: How useful are IxD patterns as physical design and evaluation aids in IxD, as compared to design guidelines? The role of guidelines and patterns as design and evaluation aids in IxD was investigated and a comparison of guidelines and patterns, based on a set of guideline and pattern properties, was conducted. The concept of pattern and guideline usefulness was explored and a research agenda for guidelines and patterns was identified, together with a set of research questions for an empirical study. The empirical study of the use of patterns for evaluation, redesign and new design, as compared to guidelines, was conducted at the Nelson Mandela Metropolitan University in 2004. The participants were a purposive sample of post-graduate Computing students, who were regarded as novice interaction designers. Two equivalent groups were formed, one that used patterns and one that used guidelines. Patterns were found to be as useful as guidelines when used as evaluation aids. Guidelines and patterns were identified as effective tools for identifying and explaining usability issues and design features. Best-effort matched sets of guidelines and patterns produced substantially different result sets when used to identify issues and features, with fairly low overlap. A substantial evaluator effect was observed for the use of guidelines and patterns for evaluation, and the results obtained were similar to those obtained by Molich et al. in their Comparative Usability Evaluation (CUE) studies. There was no statistically significant difference between the effectiveness of guidelines and patterns for evaluation. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for evaluation. Guidelines and patterns were found to be used in similar ways for evaluation. Patterns were found to be more effective than guidelines for redesign. Patterns were found to be as useful as guidelines when used for new design. There was no statistically significant difference between the effectiveness of guidelines and patterns for new design. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for redesign and new design. Guidelines and patterns were found to be used in similar ways for design. There was no statistically significant difference between the perceived usefulness of the format, content, ease of learning, and usefulness as personal and shared design languages, of guidelines and patterns. Both participant groups were equally agreeable to using guidelines and patterns in the future. The perceived usefulness of pattern collections was found to depend on the usability of the collection interface and the content quality of the patterns. The results of the empirical study thus provided empirical evidence that patterns were as useful as guidelines for evaluation and new design, and were perceived as positively as guidelines were. Patterns were found to be superior to guidelines for redesign. Patterns can therefore be used with a measure of confidence as early stage design aids for physical design and evaluation in the future. In addition to these findings, a number of opportunities for further research were identified.
- Full Text:
- Date Issued: 2009
- Authors: Cowley, Niel Lester Orr
- Date: 2009
- Subjects: Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10466 , http://hdl.handle.net/10948/1062 , Human-computer interaction , Web sites -- Design , User interfaces (Computer systems) -- Design
- Description: Design guidelines are used in interaction design (IxD) for physical design and for evaluating the usability of designs and interactive products. Guidelines are widely used for physical design and evaluation, but have a number of problems. IxD patterns have been proposed as an alternative to guidelines, as they are claimed to have several advantages over guidelines. A small number of empirical studies provide evidence that patterns are beneficial when used in IxD. Additional research on the usefulness of IxD patterns is required. The primary research question investigated in this thesis was thus: How useful are IxD patterns as physical design and evaluation aids in IxD, as compared to design guidelines? The role of guidelines and patterns as design and evaluation aids in IxD was investigated and a comparison of guidelines and patterns, based on a set of guideline and pattern properties, was conducted. The concept of pattern and guideline usefulness was explored and a research agenda for guidelines and patterns was identified, together with a set of research questions for an empirical study. The empirical study of the use of patterns for evaluation, redesign and new design, as compared to guidelines, was conducted at the Nelson Mandela Metropolitan University in 2004. The participants were a purposive sample of post-graduate Computing students, who were regarded as novice interaction designers. Two equivalent groups were formed, one that used patterns and one that used guidelines. Patterns were found to be as useful as guidelines when used as evaluation aids. Guidelines and patterns were identified as effective tools for identifying and explaining usability issues and design features. Best-effort matched sets of guidelines and patterns produced substantially different result sets when used to identify issues and features, with fairly low overlap. A substantial evaluator effect was observed for the use of guidelines and patterns for evaluation, and the results obtained were similar to those obtained by Molich et al. in their Comparative Usability Evaluation (CUE) studies. There was no statistically significant difference between the effectiveness of guidelines and patterns for evaluation. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for evaluation. Guidelines and patterns were found to be used in similar ways for evaluation. Patterns were found to be more effective than guidelines for redesign. Patterns were found to be as useful as guidelines when used for new design. There was no statistically significant difference between the effectiveness of guidelines and patterns for new design. There was also no statistically significant difference between the perceived efficiency, effectiveness and satisfaction in use of guidelines and patterns for redesign and new design. Guidelines and patterns were found to be used in similar ways for design. There was no statistically significant difference between the perceived usefulness of the format, content, ease of learning, and usefulness as personal and shared design languages, of guidelines and patterns. Both participant groups were equally agreeable to using guidelines and patterns in the future. The perceived usefulness of pattern collections was found to depend on the usability of the collection interface and the content quality of the patterns. The results of the empirical study thus provided empirical evidence that patterns were as useful as guidelines for evaluation and new design, and were perceived as positively as guidelines were. Patterns were found to be superior to guidelines for redesign. Patterns can therefore be used with a measure of confidence as early stage design aids for physical design and evaluation in the future. In addition to these findings, a number of opportunities for further research were identified.
- Full Text:
- Date Issued: 2009
Learning, governance and livelihoods : toward adaptive co-management under resource poor conditions in South Africa
- Authors: Cundill, Georgina
- Date: 2009
- Subjects: Natural resources -- Co-management -- South Africa Rural poor -- South Africa Rural development -- South Africa Households -- Economic aspects -- South Africa Sustainable development -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4747 , http://hdl.handle.net/10962/d1006961
- Description: Through collaborative monitoring and case study comparison, this thesis explores conceptual and methodological approaches to monitoring transitions toward adaptive co-management. In so doing, a number of knowledge gaps are addressed. Firstly, conceptual and methodological frameworks are developed for monitoring transitions toward adaptive co-management. Secondly, a conceptual and practical approach to monitoring the processes of collaboration and learning is developed and tested. Thirdly, a conceptual and practical approach to monitoring the governance outcomes of adaptive co-management is developed and tested. Fourthly, a conceptual and practical approach to monitoring the livelihood outcomes of adaptive co-management is developed and tested. Based on the outcomes from these four components of the study, this thesis explores the ways in which transitions toward adaptive co-management might be initiated under the resource poor conditions that characterise South Africa's communal areas. The four case studies explored in the study are described as 'resource poor' in terms of institutional capacity, ecosystem productivity and social vulnerability. From a resilience perspective these case studies can be described as being in the re-organisation phase of the adaptive cycle following multiple disturbances over time, largely due to South Africa's historical 'separate development' policies. Scholars have suggested that it is in this re-organisation phase that innovation and novelty might occur. The lens of social learning is applied to analyse collaborative processes within these contexts. Results indicate that the institutional innovation necessary for transitions toward adaptive co-management relies on careful facilitation by an 'honest broker'. Equally important is finding a balance between maintaining key individuals and knowledge holders within decision making networks, and preventing rigidity and vulnerability within communities of practice. The results point to an over simplification in the rhetoric that currently surrounds the learning outcomes of multi level networks. The governance outcomes of the initiatives are explored through the lenses of adaptive governance, social capital, adaptive capacity and self-organisation. Results indicate that under resource poor conditions creating the conditions that facilitate self-organisation is the major challenge facing transformations toward adaptive governance. Long term access to reliable information and capacity and financial support for adaptive management are key constraining variables. The livelihood outcomes of the initiatives are analysed through the lens of resilience and diversification. Results suggest that flexibility, rather than livelihood diversity, is the key livelihood strategy employed by households in situations were options are limited. Interventions that enhance opportunities for households to specialise in situ by actively dealing with structural constraints, such as access to markets and credit, is vital to encouraging innovation during transitions toward adaptive co-management. Based on the results from monitoring, this study identifies key focus areas that require a great deal more attention if transitions toward adaptive co-management are to be initiated under resource poor conditions.
- Full Text:
- Date Issued: 2009
- Authors: Cundill, Georgina
- Date: 2009
- Subjects: Natural resources -- Co-management -- South Africa Rural poor -- South Africa Rural development -- South Africa Households -- Economic aspects -- South Africa Sustainable development -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4747 , http://hdl.handle.net/10962/d1006961
- Description: Through collaborative monitoring and case study comparison, this thesis explores conceptual and methodological approaches to monitoring transitions toward adaptive co-management. In so doing, a number of knowledge gaps are addressed. Firstly, conceptual and methodological frameworks are developed for monitoring transitions toward adaptive co-management. Secondly, a conceptual and practical approach to monitoring the processes of collaboration and learning is developed and tested. Thirdly, a conceptual and practical approach to monitoring the governance outcomes of adaptive co-management is developed and tested. Fourthly, a conceptual and practical approach to monitoring the livelihood outcomes of adaptive co-management is developed and tested. Based on the outcomes from these four components of the study, this thesis explores the ways in which transitions toward adaptive co-management might be initiated under the resource poor conditions that characterise South Africa's communal areas. The four case studies explored in the study are described as 'resource poor' in terms of institutional capacity, ecosystem productivity and social vulnerability. From a resilience perspective these case studies can be described as being in the re-organisation phase of the adaptive cycle following multiple disturbances over time, largely due to South Africa's historical 'separate development' policies. Scholars have suggested that it is in this re-organisation phase that innovation and novelty might occur. The lens of social learning is applied to analyse collaborative processes within these contexts. Results indicate that the institutional innovation necessary for transitions toward adaptive co-management relies on careful facilitation by an 'honest broker'. Equally important is finding a balance between maintaining key individuals and knowledge holders within decision making networks, and preventing rigidity and vulnerability within communities of practice. The results point to an over simplification in the rhetoric that currently surrounds the learning outcomes of multi level networks. The governance outcomes of the initiatives are explored through the lenses of adaptive governance, social capital, adaptive capacity and self-organisation. Results indicate that under resource poor conditions creating the conditions that facilitate self-organisation is the major challenge facing transformations toward adaptive governance. Long term access to reliable information and capacity and financial support for adaptive management are key constraining variables. The livelihood outcomes of the initiatives are analysed through the lens of resilience and diversification. Results suggest that flexibility, rather than livelihood diversity, is the key livelihood strategy employed by households in situations were options are limited. Interventions that enhance opportunities for households to specialise in situ by actively dealing with structural constraints, such as access to markets and credit, is vital to encouraging innovation during transitions toward adaptive co-management. Based on the results from monitoring, this study identifies key focus areas that require a great deal more attention if transitions toward adaptive co-management are to be initiated under resource poor conditions.
- Full Text:
- Date Issued: 2009
Hierarchical spatial structure and levels of resolution of intertidal grazing and their consequences on predictability and stability at small scales
- Authors: Diaz Diaz, Eliecer Rodrigo
- Date: 2009
- Subjects: Marine algae -- Effect of grazing on Shorelines -- South Africa Zostera marina Intertidal ecology Spatial analysis (Statistics)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5707 , http://hdl.handle.net/10962/d1005393
- Description: The aim of this research was to assess three hierarchical aspects of alga-grazer interactions in intertidal communities on a small scale: spatial heterogeneity, grazing effects and spatial stability in grazing effects. First, using semivariograms and cross-semivariograms I observed hierarchical spatial patterns in most algal groups and in grazers. However, these patterns varied with the level on the shore and between shores, suggesting that either human exploitation or wave exposure can be a source of variability. Second, grazing effects were studied using manipulative experiments at different levels on the shore. These revealed significant effects of grazing on the low shore and in tidal pools. Additionally, using a transect of grazer exclusions across the shore, I observed unexpected hierarchical patchiness in the strength of grazing, rather than zonation in its effects. This patchiness varied in time due to different biotic and abiotic factors. In a separate experiment, the effect of mesograzers effects were studied in the upper eulittoral zone under four conditions: burnt open rock (BOR), burnt pools (Bpool), non-burnt open rock (NBOR) and non-burnt pools (NBpool). Additionally, I tested spatial stability in the effects of grazing in consecutive years, using the same plots. I observed great spatial variability in the effects of grazing, but this variability was spatially stable in Bpools and NBOR, meaning deterministic and significant grazing effects in consecutive years on the same plots. Both the significance in grazing effects and spatial stability depended on the level of resolution (species, functional, biomass) at which the algal assemblage was evaluated, suggesting hierarchical variability. In order to be able to predict spatial variability in the effects of grazers in the upper eulittoral zone using biotic and abiotic micro- and macrofactors, a conceptual model was proposed, based on data from several multiple-regressions. This linked the interactions among three elements: idiosyncratic heterogeneity, micro and macrofactors. This suggests that spatial variability can be a product of these factors, while spatial stability can be caused by the same or different combinations of factors. In conclusion, grazing and other ecological phenomena must be studied hierarchically, not only through spatiotemporal scales, but also at different levels of resolution, as these also influence our perception of patterns.
- Full Text:
- Date Issued: 2009
- Authors: Diaz Diaz, Eliecer Rodrigo
- Date: 2009
- Subjects: Marine algae -- Effect of grazing on Shorelines -- South Africa Zostera marina Intertidal ecology Spatial analysis (Statistics)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5707 , http://hdl.handle.net/10962/d1005393
- Description: The aim of this research was to assess three hierarchical aspects of alga-grazer interactions in intertidal communities on a small scale: spatial heterogeneity, grazing effects and spatial stability in grazing effects. First, using semivariograms and cross-semivariograms I observed hierarchical spatial patterns in most algal groups and in grazers. However, these patterns varied with the level on the shore and between shores, suggesting that either human exploitation or wave exposure can be a source of variability. Second, grazing effects were studied using manipulative experiments at different levels on the shore. These revealed significant effects of grazing on the low shore and in tidal pools. Additionally, using a transect of grazer exclusions across the shore, I observed unexpected hierarchical patchiness in the strength of grazing, rather than zonation in its effects. This patchiness varied in time due to different biotic and abiotic factors. In a separate experiment, the effect of mesograzers effects were studied in the upper eulittoral zone under four conditions: burnt open rock (BOR), burnt pools (Bpool), non-burnt open rock (NBOR) and non-burnt pools (NBpool). Additionally, I tested spatial stability in the effects of grazing in consecutive years, using the same plots. I observed great spatial variability in the effects of grazing, but this variability was spatially stable in Bpools and NBOR, meaning deterministic and significant grazing effects in consecutive years on the same plots. Both the significance in grazing effects and spatial stability depended on the level of resolution (species, functional, biomass) at which the algal assemblage was evaluated, suggesting hierarchical variability. In order to be able to predict spatial variability in the effects of grazers in the upper eulittoral zone using biotic and abiotic micro- and macrofactors, a conceptual model was proposed, based on data from several multiple-regressions. This linked the interactions among three elements: idiosyncratic heterogeneity, micro and macrofactors. This suggests that spatial variability can be a product of these factors, while spatial stability can be caused by the same or different combinations of factors. In conclusion, grazing and other ecological phenomena must be studied hierarchically, not only through spatiotemporal scales, but also at different levels of resolution, as these also influence our perception of patterns.
- Full Text:
- Date Issued: 2009
Application of Baylis-Hillman methodology in the construction of complex heterocyclic targets
- Ganto, Mlungiseleli MacDonald
- Authors: Ganto, Mlungiseleli MacDonald
- Date: 2009
- Subjects: Heterocyclic compounds -- Derivatives Heterocyclic chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4401 , http://hdl.handle.net/10962/d1006703
- Description: Baylis-Hillman reactions using various aromatic aldehydes, activated alkenes and catalysts have been used to: - access an extensive range of poly-heterocyclic products;explore chemoselectivity; and optimise reaction efficiency. Chromone-3-carbaldehydes and chromone-2-carbaldehydes, prepared via Vielsmeier-Haack and Kostanecki-Robinson methodology, respectively, have been used as Baylis-Hillman substrates with four different catalysts, viz., 1,4-diazabicyclo[2.2.2]octane (DABCO), 3-hydroxyquinuclidine (3-HQ), imidazole and N’,N’,N’,N’- tetramethylpropanediamine (TMPDA), and with methyl vinyl ketone (MVK), methyl acrylate, cyclic enones (2-cyclohexen-1-one, 2-cyclopenten-1-one and chromones) as activated alkenes. Reactions of the chromone- -carbaldehydes with MVK afforded dimeric Baylis-Hillman adducts when catalyzed by DABCO but when the same reactions were repeated using 3-HQ as catalyst, the dimeric products were accompanied by tricyclic Baylis-Hillman adducts. Use of excess MVK, however, led to mixtures of the normal Baylis-Hillman adducts and the tricyclic adducts – interestingly, with the apparent absence of the dimeric products. While reactions of chromone-3-carbaldehydes with methyl acrylate afforded the normal Baylis-Hillman adducts, the chromone-2- carbaldehydes produced, instead, rearrangement products, consistent with an earlier, single observation. Reactions of 2-nitrobenzaldehydes with cyclic enones using imidazole as catalyst afforded the normal Baylis-Hillman adducts, reductive cyclisation of the 2-cyclohexen-1- one and 2-cyclopenten-1-one adducts, using acetic acid and iron powder, afforded the corresponding quinoline erivatives. Treatment of cyclic enones with pyridine-2-carbaldehydes and quinoline-2-carbaldehydes using TMPDA as catalyst generally gave the expected Baylis-Hillman adducts. However, indolizine derivatives were isolated directly from Baylis-Hillman reactions involving pyridine-2-carbaldehydes and 2-cyclohexen-1-one. The remaining Baylis-Hillman adducts were cyclized to the corresponding indolizines by treatment with acetic anhydride both under reflux and under microwave-assisted conditions, the latter approach providing remarkably rapid and efficient access to the polycyclic products. Computer modelling studies have been conducted on selected polycyclic products at the Molecular Mechanics (MM), Quantum Mechanical (QM) and Density Functional (DFT) levels. The theoretical results have been used to calculate UV, IR and NMR absorption data, which have been compared, in turn, with the experimental spectroscopic data. Use has also been made of the estreNova NMR prediction programme and, generally, good agreement has been observed between the predicted and experimental spectroscopic data.
- Full Text:
- Date Issued: 2009
- Authors: Ganto, Mlungiseleli MacDonald
- Date: 2009
- Subjects: Heterocyclic compounds -- Derivatives Heterocyclic chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4401 , http://hdl.handle.net/10962/d1006703
- Description: Baylis-Hillman reactions using various aromatic aldehydes, activated alkenes and catalysts have been used to: - access an extensive range of poly-heterocyclic products;explore chemoselectivity; and optimise reaction efficiency. Chromone-3-carbaldehydes and chromone-2-carbaldehydes, prepared via Vielsmeier-Haack and Kostanecki-Robinson methodology, respectively, have been used as Baylis-Hillman substrates with four different catalysts, viz., 1,4-diazabicyclo[2.2.2]octane (DABCO), 3-hydroxyquinuclidine (3-HQ), imidazole and N’,N’,N’,N’- tetramethylpropanediamine (TMPDA), and with methyl vinyl ketone (MVK), methyl acrylate, cyclic enones (2-cyclohexen-1-one, 2-cyclopenten-1-one and chromones) as activated alkenes. Reactions of the chromone- -carbaldehydes with MVK afforded dimeric Baylis-Hillman adducts when catalyzed by DABCO but when the same reactions were repeated using 3-HQ as catalyst, the dimeric products were accompanied by tricyclic Baylis-Hillman adducts. Use of excess MVK, however, led to mixtures of the normal Baylis-Hillman adducts and the tricyclic adducts – interestingly, with the apparent absence of the dimeric products. While reactions of chromone-3-carbaldehydes with methyl acrylate afforded the normal Baylis-Hillman adducts, the chromone-2- carbaldehydes produced, instead, rearrangement products, consistent with an earlier, single observation. Reactions of 2-nitrobenzaldehydes with cyclic enones using imidazole as catalyst afforded the normal Baylis-Hillman adducts, reductive cyclisation of the 2-cyclohexen-1- one and 2-cyclopenten-1-one adducts, using acetic acid and iron powder, afforded the corresponding quinoline erivatives. Treatment of cyclic enones with pyridine-2-carbaldehydes and quinoline-2-carbaldehydes using TMPDA as catalyst generally gave the expected Baylis-Hillman adducts. However, indolizine derivatives were isolated directly from Baylis-Hillman reactions involving pyridine-2-carbaldehydes and 2-cyclohexen-1-one. The remaining Baylis-Hillman adducts were cyclized to the corresponding indolizines by treatment with acetic anhydride both under reflux and under microwave-assisted conditions, the latter approach providing remarkably rapid and efficient access to the polycyclic products. Computer modelling studies have been conducted on selected polycyclic products at the Molecular Mechanics (MM), Quantum Mechanical (QM) and Density Functional (DFT) levels. The theoretical results have been used to calculate UV, IR and NMR absorption data, which have been compared, in turn, with the experimental spectroscopic data. Use has also been made of the estreNova NMR prediction programme and, generally, good agreement has been observed between the predicted and experimental spectroscopic data.
- Full Text:
- Date Issued: 2009
Automating the conversion of natural language fiction to multi-modal 3D animated virtual environments
- Authors: Glass, Kevin Robert
- Date: 2009
- Subjects: Virtual computer systems , Virtual storage (Computer science) , Virtual reality , Computer animation , Fiction -- Computer programs , Narration (Rhetoric) -- Computer simulation , Animation (Cinematography) , Natural language processing (Computer Science)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4632 , http://hdl.handle.net/10962/d1006518
- Description: Popular fiction books describe rich visual environments that contain characters, objects, and behaviour. This research develops automated processes for converting text sourced from fiction books into animated virtual environments and multi-modal films. This involves the analysis of unrestricted natural language fiction to identify appropriate visual descriptions, and the interpretation of the identified descriptions for constructing animated 3D virtual environments. The goal of the text analysis stage is the creation of annotated fiction text, which identifies visual descriptions in a structured manner. A hierarchical rule-based learning system is created that induces patterns from example annotations provided by a human, and uses these for the creation of additional annotations. Patterns are expressed as tree structures that abstract the input text on different levels according to structural (token, sentence) and syntactic (parts-of-speech, syntactic function) categories. Patterns are generalized using pair-wise merging, where dissimilar sub-trees are replaced with wild-cards. The result is a small set of generalized patterns that are able to create correct annotations. A set of generalized patterns represents a model of an annotator's mental process regarding a particular annotation category. Annotated text is interpreted automatically for constructing detailed scene descriptions. This includes identifying which scenes to visualize, and identifying the contents and behaviour in each scene. Entity behaviour in a 3D virtual environment is formulated using time-based constraints that are automatically derived from annotations. Constraints are expressed as non-linear symbolic functions that restrict the trajectories of a pair of entities over a continuous interval of time. Solutions to these constraints specify precise behaviour. We create an innovative quantified constraint optimizer for locating sound solutions, which uses interval arithmetic for treating time and space as contiguous quantities. This optimization method uses a technique of constraint relaxation and tightening that allows solution approximations to be located where constraint systems are inconsistent (an ability not previously explored in interval-based quantified constraint solving). 3D virtual environments are populated by automatically selecting geometric models or procedural geometry-creation methods from a library. 3D models are animated according to trajectories derived from constraint solutions. The final animated film is sequenced using a range of modalities including animated 3D graphics, textual subtitles, audio narrations, and foleys. Hierarchical rule-based learning is evaluated over a range of annotation categories. Models are induced for different categories of annotation without modifying the core learning algorithms, and these models are shown to be applicable to different types of books. Models are induced automatically with accuracies ranging between 51.4% and 90.4%, depending on the category. We show that models are refined if further examples are provided, and this supports a boot-strapping process for training the learning mechanism. The task of interpreting annotated fiction text and populating 3D virtual environments is successfully automated using our described techniques. Detailed scene descriptions are created accurately, where between 83% and 96% of the automatically generated descriptions require no manual modification (depending on the type of description). The interval-based quantified constraint optimizer fully automates the behaviour specification process. Sample animated multi-modal 3D films are created using extracts from fiction books that are unrestricted in terms of complexity or subject matter (unlike existing text-to-graphics systems). These examples demonstrate that: behaviour is visualized that corresponds to the descriptions in the original text; appropriate geometry is selected (or created) for visualizing entities in each scene; sequences of scenes are created for a film-like presentation of the story; and that multiple modalities are combined to create a coherent multi-modal representation of the fiction text. This research demonstrates that visual descriptions in fiction text can be automatically identified, and that these descriptions can be converted into corresponding animated virtual environments. Unlike existing text-to-graphics systems, we describe techniques that function over unrestricted natural language text and perform the conversion process without the need for manually constructed repositories of world knowledge. This enables the rapid production of animated 3D virtual environments, allowing the human designer to focus on creative aspects.
- Full Text:
- Date Issued: 2009
- Authors: Glass, Kevin Robert
- Date: 2009
- Subjects: Virtual computer systems , Virtual storage (Computer science) , Virtual reality , Computer animation , Fiction -- Computer programs , Narration (Rhetoric) -- Computer simulation , Animation (Cinematography) , Natural language processing (Computer Science)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4632 , http://hdl.handle.net/10962/d1006518
- Description: Popular fiction books describe rich visual environments that contain characters, objects, and behaviour. This research develops automated processes for converting text sourced from fiction books into animated virtual environments and multi-modal films. This involves the analysis of unrestricted natural language fiction to identify appropriate visual descriptions, and the interpretation of the identified descriptions for constructing animated 3D virtual environments. The goal of the text analysis stage is the creation of annotated fiction text, which identifies visual descriptions in a structured manner. A hierarchical rule-based learning system is created that induces patterns from example annotations provided by a human, and uses these for the creation of additional annotations. Patterns are expressed as tree structures that abstract the input text on different levels according to structural (token, sentence) and syntactic (parts-of-speech, syntactic function) categories. Patterns are generalized using pair-wise merging, where dissimilar sub-trees are replaced with wild-cards. The result is a small set of generalized patterns that are able to create correct annotations. A set of generalized patterns represents a model of an annotator's mental process regarding a particular annotation category. Annotated text is interpreted automatically for constructing detailed scene descriptions. This includes identifying which scenes to visualize, and identifying the contents and behaviour in each scene. Entity behaviour in a 3D virtual environment is formulated using time-based constraints that are automatically derived from annotations. Constraints are expressed as non-linear symbolic functions that restrict the trajectories of a pair of entities over a continuous interval of time. Solutions to these constraints specify precise behaviour. We create an innovative quantified constraint optimizer for locating sound solutions, which uses interval arithmetic for treating time and space as contiguous quantities. This optimization method uses a technique of constraint relaxation and tightening that allows solution approximations to be located where constraint systems are inconsistent (an ability not previously explored in interval-based quantified constraint solving). 3D virtual environments are populated by automatically selecting geometric models or procedural geometry-creation methods from a library. 3D models are animated according to trajectories derived from constraint solutions. The final animated film is sequenced using a range of modalities including animated 3D graphics, textual subtitles, audio narrations, and foleys. Hierarchical rule-based learning is evaluated over a range of annotation categories. Models are induced for different categories of annotation without modifying the core learning algorithms, and these models are shown to be applicable to different types of books. Models are induced automatically with accuracies ranging between 51.4% and 90.4%, depending on the category. We show that models are refined if further examples are provided, and this supports a boot-strapping process for training the learning mechanism. The task of interpreting annotated fiction text and populating 3D virtual environments is successfully automated using our described techniques. Detailed scene descriptions are created accurately, where between 83% and 96% of the automatically generated descriptions require no manual modification (depending on the type of description). The interval-based quantified constraint optimizer fully automates the behaviour specification process. Sample animated multi-modal 3D films are created using extracts from fiction books that are unrestricted in terms of complexity or subject matter (unlike existing text-to-graphics systems). These examples demonstrate that: behaviour is visualized that corresponds to the descriptions in the original text; appropriate geometry is selected (or created) for visualizing entities in each scene; sequences of scenes are created for a film-like presentation of the story; and that multiple modalities are combined to create a coherent multi-modal representation of the fiction text. This research demonstrates that visual descriptions in fiction text can be automatically identified, and that these descriptions can be converted into corresponding animated virtual environments. Unlike existing text-to-graphics systems, we describe techniques that function over unrestricted natural language text and perform the conversion process without the need for manually constructed repositories of world knowledge. This enables the rapid production of animated 3D virtual environments, allowing the human designer to focus on creative aspects.
- Full Text:
- Date Issued: 2009
Aspects of the ecology and biology of the isopod, Exosphaeroma hylocoetes, (Barnard, 1940) in three temporarily open/closed southern African estuaries
- Authors: Henninger, Tony Oskar
- Date: 2009
- Subjects: Estuaries -- South Africa -- Eastern Cape Estuarine ecology -- South Africa -- Eastern Cape Isopoda -- South Africa -- Eastern Cape Estuarine biology -- South Africa -- Eastern Cape Ruppia maritima
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5640 , http://hdl.handle.net/10962/d1005322
- Description: Temporarily open/closed estuaries (TOCE’s) are the numerically dominant type of estuary accounting for ≈ 70 % of all estuaries along the South African coastline. Despite their numerical dominance, aspects of the biology of organisms within these systems, particularly macrocrustacea remain poorly understood. This study firstly assessed the abundance and biomass of the most common isopod, Exosphaeroma hylocoetes, in three Eastern Cape TOCE’s, (the West Kleinemonde, East Kleinemonde and Kasouga Estuaries), and their response to mouth breaching events. This study was followed by aspects of the biology of the isopod including their utilisation of submerged macrophytes as a refuge from predation and/or possible food source, as well as the growth rates of the isopods in the laboratory under different environmental conditions. Mean isopod abundances and biomasses ranged between 0 and 4 791 ind. m⁻² and 0 and 9.65 mg dwt. m⁻² in the West Kleinemonde Estuary and between 0 and 108 ind. m⁻² and 0 and 0.318 mg dwt. m⁻² in the nearby East Kleinemonde Estuary. In the Kasouga Estuary, the values ranged between 0 and 3 650 ind. m⁻² and 0 and 5.105 mg dwt. m⁻². Temporal and spatial changes in the abundance and biomass of E. hylocoetes within the three systems was primarily linked to mouth phase, with populations declining when the mouth was open and to a lesser extent, seasonality. In all three estuaries maximum isopod abundances and biomasses were recorded in their middle and upper reaches, which could be ascribed to the presence of submerged macrophytes particularly Ruppia maritima, in two of the estuaries. Males (5.71 ± 0.41 mm) were significantly larger than females (3.99 ± 0.26 mm), but the sex ratios were skewed in favour of females, (a common feature in many isopod populations). Females were found carrying brood throughout the study, releasing offspring directly into the water column, to allow recruitment to the populations. The larger the female, the larger the brood carried (up to a maximum of 72 embryo/mancas). Results of laboratory experiments indicate that the close association of Exosphaeroma hylocoetes with submerged macrophytes is a result of the plant stands providing a refuge against predation by selected ichthyofauna. However stable carbon isotope and fatty acid analyses indicate that E. hylocoetes made use of ephiphytic algae and detritus on the stems of R. maritima, rather than the submerged macrophyte itself. There were no significant differences in the growth rates of male and female isopods at combinations of temperature (15 and 25 °C) and salinity (15 and 35 ‰). Laboratory growth studies revealed that males lived longer than females (25.77 ± 3.40 weeks vs 21.52 ± 3.00 weeks), and therefore achieved larger overall size. Females, however, reached sexual maturity (at 2.5 mm) at a faster rate (two to four weeks) than males (5.5 mm after 6.5 to 11 weeks), dependent on temperature. Exosphaeroma hylocoetes with its association with submerged macrophytes, early maturity, its growth rates and longevity, female-biased sex ratios and year-round breeding, all contribute to its success in temporary open/closed estuaries.
- Full Text:
- Date Issued: 2009
- Authors: Henninger, Tony Oskar
- Date: 2009
- Subjects: Estuaries -- South Africa -- Eastern Cape Estuarine ecology -- South Africa -- Eastern Cape Isopoda -- South Africa -- Eastern Cape Estuarine biology -- South Africa -- Eastern Cape Ruppia maritima
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5640 , http://hdl.handle.net/10962/d1005322
- Description: Temporarily open/closed estuaries (TOCE’s) are the numerically dominant type of estuary accounting for ≈ 70 % of all estuaries along the South African coastline. Despite their numerical dominance, aspects of the biology of organisms within these systems, particularly macrocrustacea remain poorly understood. This study firstly assessed the abundance and biomass of the most common isopod, Exosphaeroma hylocoetes, in three Eastern Cape TOCE’s, (the West Kleinemonde, East Kleinemonde and Kasouga Estuaries), and their response to mouth breaching events. This study was followed by aspects of the biology of the isopod including their utilisation of submerged macrophytes as a refuge from predation and/or possible food source, as well as the growth rates of the isopods in the laboratory under different environmental conditions. Mean isopod abundances and biomasses ranged between 0 and 4 791 ind. m⁻² and 0 and 9.65 mg dwt. m⁻² in the West Kleinemonde Estuary and between 0 and 108 ind. m⁻² and 0 and 0.318 mg dwt. m⁻² in the nearby East Kleinemonde Estuary. In the Kasouga Estuary, the values ranged between 0 and 3 650 ind. m⁻² and 0 and 5.105 mg dwt. m⁻². Temporal and spatial changes in the abundance and biomass of E. hylocoetes within the three systems was primarily linked to mouth phase, with populations declining when the mouth was open and to a lesser extent, seasonality. In all three estuaries maximum isopod abundances and biomasses were recorded in their middle and upper reaches, which could be ascribed to the presence of submerged macrophytes particularly Ruppia maritima, in two of the estuaries. Males (5.71 ± 0.41 mm) were significantly larger than females (3.99 ± 0.26 mm), but the sex ratios were skewed in favour of females, (a common feature in many isopod populations). Females were found carrying brood throughout the study, releasing offspring directly into the water column, to allow recruitment to the populations. The larger the female, the larger the brood carried (up to a maximum of 72 embryo/mancas). Results of laboratory experiments indicate that the close association of Exosphaeroma hylocoetes with submerged macrophytes is a result of the plant stands providing a refuge against predation by selected ichthyofauna. However stable carbon isotope and fatty acid analyses indicate that E. hylocoetes made use of ephiphytic algae and detritus on the stems of R. maritima, rather than the submerged macrophyte itself. There were no significant differences in the growth rates of male and female isopods at combinations of temperature (15 and 25 °C) and salinity (15 and 35 ‰). Laboratory growth studies revealed that males lived longer than females (25.77 ± 3.40 weeks vs 21.52 ± 3.00 weeks), and therefore achieved larger overall size. Females, however, reached sexual maturity (at 2.5 mm) at a faster rate (two to four weeks) than males (5.5 mm after 6.5 to 11 weeks), dependent on temperature. Exosphaeroma hylocoetes with its association with submerged macrophytes, early maturity, its growth rates and longevity, female-biased sex ratios and year-round breeding, all contribute to its success in temporary open/closed estuaries.
- Full Text:
- Date Issued: 2009
The South African community pharmacist and Type 2 Diabetes Mellitus a pharmaceutical care intervention
- Authors: Hill, Peter William
- Date: 2009
- Subjects: Pharmacist and patient -- South Africa , Pharmaceutical services -- Patients , Pharmaceutical services -- South Africa , Pharmacists -- South Africa , Diabetes -- Treatment -- South Africa , Community health services -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3760 , http://hdl.handle.net/10962/d1003238 , Pharmacist and patient -- South Africa , Pharmaceutical services -- Patients , Pharmaceutical services -- South Africa , Pharmacists -- South Africa , Diabetes -- Treatment -- South Africa , Community health services -- South Africa
- Description: Type 2 diabetes mellitus is a chronic disease of pandemic magnitude, increasingly contributing to the disease burden of countries in the developing world, largely because of the effects of unhealthy lifestyles fuelled by unbridled urbanisation. In certain settings, patients with diabetes are more likely to have a healthcare encounter with a pharmacist than with any other healthcare provider. The overall aim of the study was to investigate the potential of South African community pharmacists to positively influence patient adherence and metabolic control in Type 2 diabetes. The designated primary endpoint was glycated haemoglobin, with the intermediate health outcomes of blood lipids, serum creatinine, blood pressure and body mass index serving as secondary endpoints. Community pharmacists and their associated Type 2 diabetes patients were recruited from areas throughout South Africa using the communication media of various nonstatutory pharmacy organisations. Although 156 pharmacists initially indicated interest in participating in the study, only 28 pharmacists and 153 patients were enrolled prior to baseline data collection. Of these, 16 pharmacists and 57 patients participated in the study for the full twelve months. Baseline clinical and psychosocial data were collected, after which pharmacists and their patients were randomised, nine pharmacists and 34 patients to the intervention group and 8 pharmacists and 27 patients to the control group. The sample size calculation revealed that each group required the participation of a minimum of 35 patients. Control pharmacists were requested to offer standard pharmaceutical care, while the intervention pharmacists were provided with a scope of practice diabetes care plan to guide the diabetes care they were to provide. Data were again collected 12-months postbaseline. At baseline, proportionally more intervention patients (82.4%) than control patients (59.3%) were using only oral anti-diabetes agents (i.e. not in combination with insulin), while insulin usage, either alone or in combination with oral agents was conversely greater in the control group (40.7%) than in the intervention group (17.6%) (Chi-squared test, p=0.013). Approximately half of the patients (53.8% control and 47.1% intervention) reported having their HbA1c levels measured in terms of accepted guidelines. There was no significant difference in HbA1c between the groups at the end of the study (Independent t-test, p=0.514). In the control group, the mean HbA1c increased from 7.3±1.2% to 7.6±1.5%, while for the intervention patients the variable remained almost constant (8.2±2.0% at baseline and 8.2±1.8% at post-baseline). Similarly, there were no significant differences between the groups with regard to any of the designated secondary clinical endpoints. Adherence to medication and self-management recommendations was similarly good for both groups. There were no significant differences between the two groups for any of the other psychosocial variables measured. In conclusion, intervention pharmacists were not able to significantly influence glycaemic control or therapeutic adherence compared to the control pharmacists.
- Full Text:
- Date Issued: 2009
- Authors: Hill, Peter William
- Date: 2009
- Subjects: Pharmacist and patient -- South Africa , Pharmaceutical services -- Patients , Pharmaceutical services -- South Africa , Pharmacists -- South Africa , Diabetes -- Treatment -- South Africa , Community health services -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3760 , http://hdl.handle.net/10962/d1003238 , Pharmacist and patient -- South Africa , Pharmaceutical services -- Patients , Pharmaceutical services -- South Africa , Pharmacists -- South Africa , Diabetes -- Treatment -- South Africa , Community health services -- South Africa
- Description: Type 2 diabetes mellitus is a chronic disease of pandemic magnitude, increasingly contributing to the disease burden of countries in the developing world, largely because of the effects of unhealthy lifestyles fuelled by unbridled urbanisation. In certain settings, patients with diabetes are more likely to have a healthcare encounter with a pharmacist than with any other healthcare provider. The overall aim of the study was to investigate the potential of South African community pharmacists to positively influence patient adherence and metabolic control in Type 2 diabetes. The designated primary endpoint was glycated haemoglobin, with the intermediate health outcomes of blood lipids, serum creatinine, blood pressure and body mass index serving as secondary endpoints. Community pharmacists and their associated Type 2 diabetes patients were recruited from areas throughout South Africa using the communication media of various nonstatutory pharmacy organisations. Although 156 pharmacists initially indicated interest in participating in the study, only 28 pharmacists and 153 patients were enrolled prior to baseline data collection. Of these, 16 pharmacists and 57 patients participated in the study for the full twelve months. Baseline clinical and psychosocial data were collected, after which pharmacists and their patients were randomised, nine pharmacists and 34 patients to the intervention group and 8 pharmacists and 27 patients to the control group. The sample size calculation revealed that each group required the participation of a minimum of 35 patients. Control pharmacists were requested to offer standard pharmaceutical care, while the intervention pharmacists were provided with a scope of practice diabetes care plan to guide the diabetes care they were to provide. Data were again collected 12-months postbaseline. At baseline, proportionally more intervention patients (82.4%) than control patients (59.3%) were using only oral anti-diabetes agents (i.e. not in combination with insulin), while insulin usage, either alone or in combination with oral agents was conversely greater in the control group (40.7%) than in the intervention group (17.6%) (Chi-squared test, p=0.013). Approximately half of the patients (53.8% control and 47.1% intervention) reported having their HbA1c levels measured in terms of accepted guidelines. There was no significant difference in HbA1c between the groups at the end of the study (Independent t-test, p=0.514). In the control group, the mean HbA1c increased from 7.3±1.2% to 7.6±1.5%, while for the intervention patients the variable remained almost constant (8.2±2.0% at baseline and 8.2±1.8% at post-baseline). Similarly, there were no significant differences between the groups with regard to any of the designated secondary clinical endpoints. Adherence to medication and self-management recommendations was similarly good for both groups. There were no significant differences between the two groups for any of the other psychosocial variables measured. In conclusion, intervention pharmacists were not able to significantly influence glycaemic control or therapeutic adherence compared to the control pharmacists.
- Full Text:
- Date Issued: 2009
Patterns and determinants of species richness in mesic temparate grasslands of South Africa
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
Photophysical and photochemical behaviour of metallophthalocyanines effect of nanoparticles and molecules of biological importance
- Authors: Idowu, Mopelola Abidemi
- Date: 2009
- Subjects: Electrochemistry Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4329 , http://hdl.handle.net/10962/d1004990
- Description: Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.
- Full Text:
- Date Issued: 2009
- Authors: Idowu, Mopelola Abidemi
- Date: 2009
- Subjects: Electrochemistry Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4329 , http://hdl.handle.net/10962/d1004990
- Description: Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.
- Full Text:
- Date Issued: 2009
Advances in platinum-amine chemotherapeutic agents : their chemistry and applicationc
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
- Authors: Jaganath, Yatish
- Date: 2009
- Subjects: Coordination compounds , Antineoplastic antibiotics , Cancer -- Chemotherapy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10446 , http://hdl.handle.net/10948/d1021222
- Description: The research conducted in this study focussed on advancing the knowledge database of diamineplatinum complexes on two frontiers: 1) the development of novel anticancer complexes, and 2) improvements in their synthetic chemistry. Novel square-planar dichloro and oxalato platinum(II) complexes were synthesized as potential anticancer agents in accordance with a comprehensive set of factors identified as being significant in optimizing such action. The nonleaving ligands consisted of asymmetric chelating chiral diamines of the form 1- (1-R-imidazol-2yl)(R')methanamine (R representing methyl, butyl and R' methyl, phenyl). The complexes were characterized by a host of spectral, thermal and crystallographic techniques. In addition, the stabilities of the complexes were monitored in aqueous and saline solutions. Cytotoxicity screening on three cultured cancer cell lines (MCF-7, HeLa and HT29) indicated the compounds, present as their respective racemates, to have rather modest activities relative to cisplatin; with complexes having the smallest substituents, R,R' = methyl, being most active. In recognition of the limitations of traditional silver-based syntheses of oxalatoplatinum(II) complexes, innovative non-silver methods were developed using the well known cancer drug, oxaliplatin, (trans-R,R-1,2- diaminocyclohexane)oxalatoplatinum(II), as a prototype. These involved direct ligand exchange reactions of the dichloro precursor, (trans-R,R-1,2- diaminocyclohexane)dichloroplatinum(II), with tetrabutylammonium oxalate in essentially non-aqueous solvents. A 90:10 mixture of isoamyl alcohol (3-methyl- 1-butanol):water, proved to be a promising solvent, enabling the recovery of pure oxaliplatin (~98 percent) after 9 hours at 88 °C in yields of up to 86 percent. In light of the perceived unique mode of anticancer action available to mononitroplatinum(IV) complexes (i.e. their STAT3-binding potential), octahedral diamineoxalatoplatinum(IV) complexes containing axially-coordinated nitro and halo co-ligands were synthesized and extensively characterized. Electrochemical studies revealed trends in reduction potential which could be correlated to structural / chemical traits of the coordinated diamine and axial ligands. The similarities of the determined cytotoxicities of the platinum(IV) compounds and their respective platinum(II) analogues, implicated reduction as a means of activation of the platinum(IV) complexes.
- Full Text:
- Date Issued: 2009
The impact of HIV and AIDS on household food security and food acquisition strategies in South Africa
- Authors: Kaschula, S A H
- Date: 2009
- Subjects: Food security -- South Africa Food supply -- South Africa AIDS (Disease) -- Social aspects -- South Africa HIV infections -- Social aspects -- South Africa Chronically ill -- Economic conditions -- South Africa Chronically ill -- Social conditions -- South Africa Food -- Social aspects -- South Africa Food -- Economic aspects -- South Africa Rural development -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4754 , http://hdl.handle.net/10962/d1007137
- Description: How should the impact of HIV and AIDS on rural livelihoods be factored into efforts to monitor and stabilise household food security? With both HIV and AIDS and food security at the top of the global development agenda, this is a question posed by many scholars, practitioners, donor agencies and government departments. However, while there is an excess of discourse outlining the theoretical bases for how HIV and AIDS can, and is, radically transforming household food acquisition; there is a lack of empirical evidence from the South African context that demonstrates if, and how, HIV and AIDS changes household-level strategies of food acquisition and intake. This thesis explores the association of household-level mortality, chronic illness and additional child-dependent fostering with household experience of food security and food acquisition strategies, in three rural villages in the Eastern Cape and KwaZulu-Natal Provinces of South Africa. Qualitative and quantitative methods of data-collection were applied to 307 households in the three sites. For twelve months, both HIV and AIDS-afflicted and non-afflicted households were repeatedly visited at 3-month intervals, in order to be assessed for levels of food security, dietary intake and method of food procurement (purchased, cultivated, wild or donated). Overall, HIV and AIDS-afflicted households showed a significantly higher experience of food insecurity, probably attributable to shortages in food quantity. Dietary composition and overall diversity, however, was not significantly different. Although households with chronic illness and recent mortality showed a heightened investment in cultivation sources, the success of these strategies were to a great extent mediated by household income, and the level of medical treatment received by those who were chronically ill. Chronic illness was also associated with more donations, but these required considerable investments in social capital networks. Finally, use of wild leafy vegetables was not associated with household HIV and AIDS status, despite the financial, nutritional and labour-saving properties of these foods. Overall, the study suggests that there was little evidence of long-term planning and strategy in household food security responses. There was no evidence for shifts to labour-saving crops or foods and, in some instances, child labour was being used to ameliorate prime-adult labour deficits. Moreover, given that the vast majority (89.2%) of food groups were sourced through purchase, it is questionable whether investing in diverse food acquisition strategies would be advisable. Unless supported by medical treatment and steady earned household income, policies to promote intensified household agricultural subsistence production in the wake of HIV and AIDS are unlikely to provide households with anything more than short-term safety-nets, rather than long-term, sustainable food security solutions.
- Full Text:
- Date Issued: 2009
- Authors: Kaschula, S A H
- Date: 2009
- Subjects: Food security -- South Africa Food supply -- South Africa AIDS (Disease) -- Social aspects -- South Africa HIV infections -- Social aspects -- South Africa Chronically ill -- Economic conditions -- South Africa Chronically ill -- Social conditions -- South Africa Food -- Social aspects -- South Africa Food -- Economic aspects -- South Africa Rural development -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4754 , http://hdl.handle.net/10962/d1007137
- Description: How should the impact of HIV and AIDS on rural livelihoods be factored into efforts to monitor and stabilise household food security? With both HIV and AIDS and food security at the top of the global development agenda, this is a question posed by many scholars, practitioners, donor agencies and government departments. However, while there is an excess of discourse outlining the theoretical bases for how HIV and AIDS can, and is, radically transforming household food acquisition; there is a lack of empirical evidence from the South African context that demonstrates if, and how, HIV and AIDS changes household-level strategies of food acquisition and intake. This thesis explores the association of household-level mortality, chronic illness and additional child-dependent fostering with household experience of food security and food acquisition strategies, in three rural villages in the Eastern Cape and KwaZulu-Natal Provinces of South Africa. Qualitative and quantitative methods of data-collection were applied to 307 households in the three sites. For twelve months, both HIV and AIDS-afflicted and non-afflicted households were repeatedly visited at 3-month intervals, in order to be assessed for levels of food security, dietary intake and method of food procurement (purchased, cultivated, wild or donated). Overall, HIV and AIDS-afflicted households showed a significantly higher experience of food insecurity, probably attributable to shortages in food quantity. Dietary composition and overall diversity, however, was not significantly different. Although households with chronic illness and recent mortality showed a heightened investment in cultivation sources, the success of these strategies were to a great extent mediated by household income, and the level of medical treatment received by those who were chronically ill. Chronic illness was also associated with more donations, but these required considerable investments in social capital networks. Finally, use of wild leafy vegetables was not associated with household HIV and AIDS status, despite the financial, nutritional and labour-saving properties of these foods. Overall, the study suggests that there was little evidence of long-term planning and strategy in household food security responses. There was no evidence for shifts to labour-saving crops or foods and, in some instances, child labour was being used to ameliorate prime-adult labour deficits. Moreover, given that the vast majority (89.2%) of food groups were sourced through purchase, it is questionable whether investing in diverse food acquisition strategies would be advisable. Unless supported by medical treatment and steady earned household income, policies to promote intensified household agricultural subsistence production in the wake of HIV and AIDS are unlikely to provide households with anything more than short-term safety-nets, rather than long-term, sustainable food security solutions.
- Full Text:
- Date Issued: 2009
Racism and law : implementing the right to equality in selected South African equality courts
- Authors: Krüger, Rósaan
- Date: 2009
- Subjects: South Africa Promotion of Equality and Prevention of Unfair Discrimination Act, 2000 , Equality -- South Africa , Discrimination -- Law and legislation -- South Africa , Racism -- Law and legislation -- South Africa , Apartheid -- Law and legislation -- South Africa , Constitutional law -- South Africa , South Africa -- Politics and government -- 1994-
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3677 , http://hdl.handle.net/10962/d1003192 , South Africa Promotion of Equality and Prevention of Unfair Discrimination Act, 2000 , Equality -- South Africa , Discrimination -- Law and legislation -- South Africa , Racism -- Law and legislation -- South Africa , Apartheid -- Law and legislation -- South Africa , Constitutional law -- South Africa , South Africa -- Politics and government -- 1994-
- Description: Racism has informed South African society since colonial times. Racist beliefs found expression in the laws of colonial and apartheid South Africa and shaped both state and society. The constitutional state that South Africa has become since 1994, is based on the values of ‘human dignity’, ‘the achievement of equality’ and ‘nonracialism’, among others. Law formed the basis of the racist state prior to 1994, and now law has a fundamental role to play in the transformation of the state and society in an egalitarian direction by addressing socio-economic inequalities on the one hand, and by changing patterns of behaviour based on racist beliefs forged in the past, on the other. This thesis examines one of the legal instruments that is intended to contribute to transformation in the latter sense, namely the Promotion of Equality and Prevention of Unfair Discrimination Act 4 of 2000 (the Equality Act), with specific reference to the issue of racism. The provisions of this Act and the framework for its operation against the background of South Africa’s racist past, and within the broader framework of international and constitutional law, are examined. These two legal frameworks are analysed for the purpose of determining the standards set by international and constitutional law regarding racial equality in order to determine whether the Equality Act measures up. This thesis also incorporates an analysis of the practical application of the provisions of the Equality Act to complaints of racism in selected equality courts. The theoretical analysis of the Act’s provisions and their application in the equality courts point to various problematic formulations and obstacles which negatively affect the application of the provisions and thus hamper social change. The thesis concludes with recommendations for refining the Act’s provisions and its application.
- Full Text:
- Date Issued: 2009
- Authors: Krüger, Rósaan
- Date: 2009
- Subjects: South Africa Promotion of Equality and Prevention of Unfair Discrimination Act, 2000 , Equality -- South Africa , Discrimination -- Law and legislation -- South Africa , Racism -- Law and legislation -- South Africa , Apartheid -- Law and legislation -- South Africa , Constitutional law -- South Africa , South Africa -- Politics and government -- 1994-
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3677 , http://hdl.handle.net/10962/d1003192 , South Africa Promotion of Equality and Prevention of Unfair Discrimination Act, 2000 , Equality -- South Africa , Discrimination -- Law and legislation -- South Africa , Racism -- Law and legislation -- South Africa , Apartheid -- Law and legislation -- South Africa , Constitutional law -- South Africa , South Africa -- Politics and government -- 1994-
- Description: Racism has informed South African society since colonial times. Racist beliefs found expression in the laws of colonial and apartheid South Africa and shaped both state and society. The constitutional state that South Africa has become since 1994, is based on the values of ‘human dignity’, ‘the achievement of equality’ and ‘nonracialism’, among others. Law formed the basis of the racist state prior to 1994, and now law has a fundamental role to play in the transformation of the state and society in an egalitarian direction by addressing socio-economic inequalities on the one hand, and by changing patterns of behaviour based on racist beliefs forged in the past, on the other. This thesis examines one of the legal instruments that is intended to contribute to transformation in the latter sense, namely the Promotion of Equality and Prevention of Unfair Discrimination Act 4 of 2000 (the Equality Act), with specific reference to the issue of racism. The provisions of this Act and the framework for its operation against the background of South Africa’s racist past, and within the broader framework of international and constitutional law, are examined. These two legal frameworks are analysed for the purpose of determining the standards set by international and constitutional law regarding racial equality in order to determine whether the Equality Act measures up. This thesis also incorporates an analysis of the practical application of the provisions of the Equality Act to complaints of racism in selected equality courts. The theoretical analysis of the Act’s provisions and their application in the equality courts point to various problematic formulations and obstacles which negatively affect the application of the provisions and thus hamper social change. The thesis concludes with recommendations for refining the Act’s provisions and its application.
- Full Text:
- Date Issued: 2009
Characterisation of Trypanosomal Type III and Type IV Hsp40 proteins
- Louw, Cassandra Alexandrovna
- Authors: Louw, Cassandra Alexandrovna
- Date: 2009
- Subjects: Trypanosoma Heat shock proteins African trypanosomiasis Epidemic encephalitis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3926 , http://hdl.handle.net/10962/d1003985
- Description: The heat shock protein-70 (Hsp70) family of molecular chaperones are ubiquitous highly conserved proteins that are critical for the viability of cellular homeostasis. The ATPase activity of Hsp70 proteins is critical to their function as the affinity of a given Hsp70 for non-native substrate is modulated by ATP binding and hydrolysis. When bound to ATP, Hsp70s possess a low affinity for a given substrate protein, while the hydrolysis of ATP to ADP causes a conformational change that results in a high affinity for substrate proteins. The basal ATPase activity of Hsp70s is too low to facilitate their function in vivo, and co-chaperones are essential to modulate the efficient protein folding by Hsp70. Heat shock protein-40 (Hsp40) heat shock proteins are essential for the in vivo function of Hsp70s by stimulating the ATPase activity of these proteins and facilitating transfer of substrates. The Type III class of Hsp40 proteins have not been well characterised due to their poor levels of conservation at the primary sequence level. This is due to the fact that Type III Hsp40s only contain a J-domain and a poorly conserved C-terminal region. The newly identified Type IV class of Hsp40s, contain an abrogated HPD tripeptide motif in the J-domain and have also not been extensively studied. Trypanosoma brucei (T. brucei) is a unicellular flagellated protozoan parasite. It is the causative agent of Human African Trypansomiasis (HAT) which results in thousands of deaths and devastating agricultural losses in many parts of Africa. T. brucei undergoes a complex lifecycle that is characterised by the transition from an insect vector to a mammalian host in markedly different conditions of temperature, pH, nutrient availability and respiratory requirements. It has been proposed that molecular chaperones may enhance the survival of these parasites due to their cytoprotective effect in combating cellular stress. Due to the fact that T. brucei infection is invariably fatal if left untreated, and that no novel treatment regimens have been developed recently, the identification of potential novel drug targets among proteins essential to the parasite’s survival in the host organism is an attractive aspect of T. brucei research. Because Type III Hsp40s are poorly conserved with respect to Hsp40s found in the human host, the identification of any of these proteins found to be essential to T. brucei survival in humans could potentially make attractive novel drug targets. An in depth in silico investigation into the Type III Hsp40 complement as well as partner Hsp70 proteins in T.brucei was performed. T. brucei possesses 65 Hsp40 proteins, of which 47 were classed as Type III and 6 of which were identified as being putative Type IV Hsp40s. A small but significant number (5) of Type III TbHsp40s contained tetratricopeptide (TPR) domains in addition to the J-domain. The J-domains of the Type III TbHsp40 complement were found to be conserved with respect to those of canonical Hsp40 proteins, although the mutation of certain residues that play a key role in Hsp40-Hsp70 interaction was noted. Potential partnerships of these proteins in the parasite was also investigated. The coding regions of three previously uncharacterised TbHsp40s were successfully amplified from T. brucei TREU927 genomic DNA and cloned into an expression vector. Tbj1, a Tcj1 ortholog, was selected for further study and successfully expressed and biochemically characterised. Tbj1 expressed in E. coli was found to be insoluble, but large amounts were recovered with the aid of a denaturing purification followed by refolding elution strategies, and the bulk of the protein recovered was in compact monomeric form as determined by size-exclusion chromatography fast protein liquid chromatography (SEC-FPLC). The addition of Tbj1 to a thermally aggregated substrate resulted in increased levels of aggregation, although Tbj1 was able to assist two Hsp70 proteins in the suppression of aggregation. Tbj1 proved unable to stimulate the ATPase activity of these same Hsp70s, and could not rescue temperature sensitive cells when replacing E.coli DnaJ and CbpA. It was concluded that Tbj1 does not possess independent chaperone activity, but could display Hsp40 co-chaperone properties under certain circumstances. This could allude to a specialised function in the T. brucei parasite. The lack of human orthologues to Tbj1 could result in the attractiveness of this protein as a novel drug target.
- Full Text:
- Date Issued: 2009
- Authors: Louw, Cassandra Alexandrovna
- Date: 2009
- Subjects: Trypanosoma Heat shock proteins African trypanosomiasis Epidemic encephalitis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3926 , http://hdl.handle.net/10962/d1003985
- Description: The heat shock protein-70 (Hsp70) family of molecular chaperones are ubiquitous highly conserved proteins that are critical for the viability of cellular homeostasis. The ATPase activity of Hsp70 proteins is critical to their function as the affinity of a given Hsp70 for non-native substrate is modulated by ATP binding and hydrolysis. When bound to ATP, Hsp70s possess a low affinity for a given substrate protein, while the hydrolysis of ATP to ADP causes a conformational change that results in a high affinity for substrate proteins. The basal ATPase activity of Hsp70s is too low to facilitate their function in vivo, and co-chaperones are essential to modulate the efficient protein folding by Hsp70. Heat shock protein-40 (Hsp40) heat shock proteins are essential for the in vivo function of Hsp70s by stimulating the ATPase activity of these proteins and facilitating transfer of substrates. The Type III class of Hsp40 proteins have not been well characterised due to their poor levels of conservation at the primary sequence level. This is due to the fact that Type III Hsp40s only contain a J-domain and a poorly conserved C-terminal region. The newly identified Type IV class of Hsp40s, contain an abrogated HPD tripeptide motif in the J-domain and have also not been extensively studied. Trypanosoma brucei (T. brucei) is a unicellular flagellated protozoan parasite. It is the causative agent of Human African Trypansomiasis (HAT) which results in thousands of deaths and devastating agricultural losses in many parts of Africa. T. brucei undergoes a complex lifecycle that is characterised by the transition from an insect vector to a mammalian host in markedly different conditions of temperature, pH, nutrient availability and respiratory requirements. It has been proposed that molecular chaperones may enhance the survival of these parasites due to their cytoprotective effect in combating cellular stress. Due to the fact that T. brucei infection is invariably fatal if left untreated, and that no novel treatment regimens have been developed recently, the identification of potential novel drug targets among proteins essential to the parasite’s survival in the host organism is an attractive aspect of T. brucei research. Because Type III Hsp40s are poorly conserved with respect to Hsp40s found in the human host, the identification of any of these proteins found to be essential to T. brucei survival in humans could potentially make attractive novel drug targets. An in depth in silico investigation into the Type III Hsp40 complement as well as partner Hsp70 proteins in T.brucei was performed. T. brucei possesses 65 Hsp40 proteins, of which 47 were classed as Type III and 6 of which were identified as being putative Type IV Hsp40s. A small but significant number (5) of Type III TbHsp40s contained tetratricopeptide (TPR) domains in addition to the J-domain. The J-domains of the Type III TbHsp40 complement were found to be conserved with respect to those of canonical Hsp40 proteins, although the mutation of certain residues that play a key role in Hsp40-Hsp70 interaction was noted. Potential partnerships of these proteins in the parasite was also investigated. The coding regions of three previously uncharacterised TbHsp40s were successfully amplified from T. brucei TREU927 genomic DNA and cloned into an expression vector. Tbj1, a Tcj1 ortholog, was selected for further study and successfully expressed and biochemically characterised. Tbj1 expressed in E. coli was found to be insoluble, but large amounts were recovered with the aid of a denaturing purification followed by refolding elution strategies, and the bulk of the protein recovered was in compact monomeric form as determined by size-exclusion chromatography fast protein liquid chromatography (SEC-FPLC). The addition of Tbj1 to a thermally aggregated substrate resulted in increased levels of aggregation, although Tbj1 was able to assist two Hsp70 proteins in the suppression of aggregation. Tbj1 proved unable to stimulate the ATPase activity of these same Hsp70s, and could not rescue temperature sensitive cells when replacing E.coli DnaJ and CbpA. It was concluded that Tbj1 does not possess independent chaperone activity, but could display Hsp40 co-chaperone properties under certain circumstances. This could allude to a specialised function in the T. brucei parasite. The lack of human orthologues to Tbj1 could result in the attractiveness of this protein as a novel drug target.
- Full Text:
- Date Issued: 2009