Integrated Algae Pond Systems for the Treatment of Municipal Wastewater
- Authors: Mambo, Mutsa Prudence
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5960 , http://hdl.handle.net/10962/d1021258
- Description: Integrated algae pond systems are a derivation of the Oswald designed advanced integrated wastewater ponding system, and combine the use of anaerobic and aerobic bioprocesses to effect wastewater treatment. Integrated algae pond system technology was introduced to South Africa in 1996 and a pilot plant was designed and commissioned at the Belmont Valley wastewater treatment works in Grahamstown. Previous studies showed that this system delivered a final effluent superior to most pond systems deployed in South Africa but that it was unable to meet the general standard for nutrient removal and effluent discharge. This study was initiated to re-appraise integrated algae pond systems and to assess the potential of the technology as an effective municipal sewage treatment system. And more...
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Investigating the nature of the linguistic challenges of the Department of Basic Education (DBE) 2013 Grade 4 Mathematics ANAs and learners’ and teachers’ experience of them.
- Authors: Sibanda, Lucy
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2079 , http://hdl.handle.net/10962/d1021312
- Description: The underperformance of South African learners in literacy and numeracy is a source of grave concern, especially at the transition from Grade 3 to Grade 4. The challenge that complicates this shift is to some extent linguistic, since at Grade 4 in South Africa the majority of learners begin learning in English, which is an additional language for most. The study adopts a sociocultural view of language and learning. Vygotsky’s influential theoretical work on language and learning, in which language is considered central to learning and learning is a social process embedded in sociocultural settings, informs the study. The introduction of the Annual National Assessments (ANAs) across primary and secondary grades in South Africa in mathematics and literacy in 2011 provides the context for this research. It is against this background that the present study aimed, through a case study approach of three Grade 4 classes of English additional language (EAL) learners, to achieve four things, namely: to investigate the linguistic challenges of the 2013 Grade 4 mathematics ANAs; to analyse the learners’ written responses to the 2013 mathematics ANA items; to explore the 2013 Grade 4 learners’ difficulties and experiences of the 2013 mathematics ANAs, and to investigate the Grade 4 mathematics teachers’ perspectives of the language of the ANAs. In order to achieve these aims, the data was collected in four phases. The first phase of the study addressed the nature of the linguistic challenges of the Department of Basic Education Grade 4 mathematics ANAs. Data collection occurred in two parts: 1) Comparing Grade 4 ANAs to exemplars provided and 2) Analysing the language of the 2013 mathematics ANAs. This was done through content analysis and Shaftel et al.’s (2006) linguistic complexity checklist. Findings for part 1 of the study revealed that there were several inconsistencies in the questioning format and language used in the ANAs and in the exemplars. Findings of the content analysis done on the 2013 mathematics ANA test items using Shaftel et al.’s (2006) linguistic complexity checklist and Vale’s (2013) Linguistic Complexity Index formula point to many linguistic complexities in several test items, particularly in relation to recurrent use of: 7 or more letter words, homophones, prepositional phrases and specific mathematics vocabulary across the majority of questions. In phase 2, the analysis of 106 learners’ written responses for the 2013 mathematics ANA questions revealed that for many of the questions the language used was unfamiliar for Grade 4 learners using English as an additional language. This was aggravated by the inclusion in the ANAs of linguistic forms learners would not have encountered in their workbooks or exemplars intended to prepare the learners for the assessments. Therefore, linguistic complexity of items was a key contributing factor to learners’ poor performance in the test. In the third phase, the quantitative and qualitative analysis of the 26 learners’ interviews revealed that during the task-based interviews, learners experienced difficulties in the following skills: reading, comprehension, transformation, process and encoding. The greatest difficulties were experienced in comprehension and in reading, especially in the two classes where the learners were less proficient in the English language. The fourth phase, in which two Grade 4 mathematics teachers’ perceptions of the linguistic demands of the Grade 4 mathematics ANAs were presented and analysed, the teachers’ perceptions indicated that the mathematical language was mostly too difficult for the Grade 4 learners. Teachers also were of the opinion that learners’ reading skills were poor and they struggled to comprehend what they read. A dilemma regarding whether teachers should assist learners during the ANAs, satisfying the local needs for mediating the language or whether they should comply with the ANA policy which states that they may not assist learners was expressed by one of the teachers. A range of language challenges that teachers managed with various strategies were raised. These included one teacher’s use of code-switching during the teaching of mathematics. The study concludes with implications and recommendations. These include that test designers should minimise the language complexity of test items, especially in the early transition grades of learning in English. Research should be conducted on possibilities for allowing teachers to provide linguistic mediation to ANA questions in these transition years of learners learning in English.
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Land-use effects on mammal communities in the Fish-Kowie corridor, Eastern Cape, South Africa, with particular reference to carnivores
- Authors: Kok, Armand du Preez
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/561 , vital:19970
- Description: Human population growth is causing an increase in habitat transformation on a global scale, and this transformation is driven by changes in land-use practices. One consequence of habitat transformation is the negative effect it can have on mammal communities, especially carnivores. Carnivores are important components of ecosystems as they play an essential structuring role, but also often come into conflict with people. I studied the impact of land-use on mammalian diversity, the attitudes of landowners/managers towards carnivores, the distribution of carnivores, and the interactions among carnivore species in the Fish-Kowie corridor (FKC), an area of conservation concern, in the Eastern Cape, South Africa. Livestock and game farming are the two dominant land-use types in the FKC. Carnivore distribution data were collected between 2012 and 2014 using a robust camera trap survey that consisted of 432 camera stations (216 on livestock and 216 on game farms). In addition, the attitudes of 55 landowners/managers were assessed using semi- structured questionnaire interviews that were conducted in person. My results revealed that mammal diversity was similar on the two land-use types. However, individual species differed in their distribution on the two land-use types. In general, both livestock and game farmers had negative attitudes towards carnivores in the FKC, due to their depredation of valuable livestock and game species. Black-backed jackals (Canis mesomelas), caracals (Caracal caracal), leopards (Panthera pardus), and brown hyaenas (Parahyaena brunnea) were considered the most problematic carnivores, but sensitivity to land-use varied among these four species. Black- backed jackals had the highest occupancy rates of all four predators and were 3.8 times more likely to occupy sites on game farms compared to livestock farms. By contrast, leopards and brown hyaenas were only detected on game farms, and caracals did not appear to be sensitive to the effects of land-use. In general, the interactions among carnivores were weak and were likely driven by carnivore diversity, resource partitioning, and anthropogenic pressures. While there were many subtle differences in the distribution of mammal species and human attitudes towards wildlife on livestock and game farms in the FKC, there were also many similarities. My study has produced results that can be used by the FKC community to better understand how mammals and humans interact across the landscape, information that will ultimately contribute to future conservation planning in the area.
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Life history of the maritime platygastrid Echthrodesis lamorali Masner 1968 (Hymenoptera: Platygastridae: Scelioninae)
- Authors: Owen, Candice Ann
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/837 , vital:19995 , 10.21504/10962/837
- Description: Echthrodesis lamorali Masner 1968 (Hymenoptera: Platygastridae, Scelioninae) is an intertidal parasitoid wasp that uses the eggs of the maritime spider, Desis formidabilis O.P. Cambridge 1890 (Araneae: Desidae), as a host. This species is one of only three known maritime parasitoids globally, and is the only known spider egg parasitoid that attacks its host within the intertidal region in southern Africa. Originally described from ‘The Island’, Kommetjie (Western Cape, South Africa), this shore was the only known locality of the species at the commencement of this thesis. Furthermore, the extent of the parasitism pressure the wasp exerts on D. formidabilis was largely unknown, along with its basic biology (drivers of its broad-scale and fine-scale distribution patterns; parasitism incidence; and sex ratios) and morphological and physiological adaptations for living within the frequently saltwater-inundated environment. This thesis unravelled these aspects, as well as experimentally provided data for many components of the life history of E. lamorali that had only been hypothesized by other authors, at a variety of scales, from the country-wide ecosystem, to single shores, and finally to the scale of the individual. While the distribution of E. lamorali was found to be much wider than previously thought, it remained restricted to the shores of the Cape Peninsula (Western Cape, South Africa). The host spiders were located throughout a much wider distributional range than the wasp, from East London in the east to the Peninsula, but some behavioural and morphological differences were found between those within and outside of the range of the parasitoid, suggesting range-limitation imposed by the host on E. lamorali. This limitation may be strengthened by the general lack of suitable shore types within the close vicinity of the Peninsula. Modelling using macro-climatic conditions suggested that maximum temperatures and humidities were also largely limiting to E. lamorali, although these patterns were not observable in the micro-climates in which the species survives. The wasp populations and spiders within the range of E. lamorali as identified in Chapter 2 were assessed to determine any preferences for local conditions, including location along the Peninsula, nesting sites and intertidal zones within single shores, using AICc modelling, which detected parasitism patterns in D. formidabilis and E. lamorali populations, as well as the sex ratios in the latter species. The models showed that the spider population size and distribution was more influenced by bottom-up factors such as abiotic components of the shore than by parasitism, which only showed density dependence with the host at certain scales. Both host and parasitoid populations illustrated a preference for the middle zone on single shores. Observed spider nest characteristics suggested opportunistic nesting behaviour in the species, although preference was shown for construction along an east-west orientation and in locations with low sun exposure. Along with larger population sizes on the west coast over the east coast (not reflected by E. lamorali), these observations suggest that D. formidabilis prefers cooler environments. Spider brood success was 50% in unparasitized egg-sacs, but this figure halved when E. lamorali gained access to the eggs (of which 100% within a single compartment were parasitized each time). Encapsulation of the embryo was found to be positively correlated with parasitism, indicating some form of host resistance. Resultant parasitoid broods illustrated a strong female bias in the species, as is common for this group of insects. The life history of E. lamorali was then assessed at a smaller scale, that of the individual. Scanning electron microscopy of whole E. lamorali specimens and light microscopy of sectioned specimens demonstrated no morphological adaptations in the trachea and spiracles to cope with saltwater inundation. On the other hand, respirometry experiments categorically demonstrated that the species copes with inundation through the formation of a physical gill over the full habitus, and the induction of a state of torpor to reduce metabolic needs, when submerged. This precludes the need for any further morphological adaptations. Determination of the wasp’s critical thermal tolerance illustrated a wide temperature range with a particularly cold lower limit of -1.1ºC ± 0.16, suggesting the presence of related genera or ancestors in much colder environments. With a much broader distribution than previously thought, and the inclusion of the distributional range of E. lamorali within the Table Mountain National Park, this species is being effectively conserved and managed through the umbrella-conservation of the park. Links to the host proved to vary at differing scales, proving the need for scale considerations to be included in other similar biological and ecological studies. Finally, the species showed physiological adaptation to its intertidal existence. Echthrodesis lamorali, the only discovered maritime spider egg parasitoid in Southern Africa, displayed unusual characteristics at every scale of its life history and as such, warrants further investigation.
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Links between valley confinement, landforms and vegetation distribution in a semi-arid valley floor environment, Baviaanskloof, South Africa
- Authors: Smith-Adao, Lindie B
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/953 , vital:20006
- Description: Although a large body of international literature has advanced our understanding of river systems, a considerable amount of gaps exit in the knowledge of dryland systems. River systems reflect complex interactions between biophysical processes and patterns. Understanding how processes generate observed patterns and, in turn, how patterns influence processes is crucial to understanding river structure and function. It requires an interdisciplinary approach in both research and resulting applications. The aim of this thesis was to examine the relationship between valley confinement, fluvial style, valley floor morphology and vegetation in the semi-arid environment of the Baviaanskloof river catchment, South Africa. This interdisciplinary investigation used a mixed method approach that involved desktop analyses and field surveys to understand dynamics at multiple scales, from the whole catchment to local (site, reach and quadrat or sample plot) scales. The desktop analyses included historical rainfall patterns and climate extremes, aerial photograph time-series and remote sensing greenness indices, and the field surveys focussed on cross-valley landform profiles, groundwater depth levels, sediment size distribution and soil chemistry, and vegetation distribution patterns. Based on the integrative assessment of these techniques a framework was developed of the links between valley confinement, surface-groundwater interaction, hydrogeomorphic processes and landforms, vegetation and human activities. Study findings highlighted the fact that very strong links exist between these factors. In this semi-arid area water availability (groundwater and streamflow conditions) was the primary control on valley floor vegetation composition and patterning. One group of species was associated with the wetted channel reaches at confined and semi-confined valley settings, while the other was associated with dry bed channel reaches at unconfined valley settings. The analyses also indicated that the environmental variables which best explained the variation in vegetation at the differing geomorphic landforms were related to landform position (elevation and distance), sediment size (fine and coarse sand) and available phosphorus (i.e. human impacts). The different plants, in turn, also affected landforms through their influence on sediment erosion, transport and deposition. Specially, they build, maintained or modified geomorphic landforms at confined, semi-confined and unconfined valley settings across the valley floor. Valley confinement was a primary control influencing hydrogeomorphic processes and their associated landforms. Alluvial fans and terraces acted as critical additional controls at especially the unconfined valley setting. Implications for restoration efforts in the catchment included strategies that took cognisance of: active revegetation on floodplain surfaces related to former agricultural fields; channel switching associated with the highly dynamic and unpredictable nature of geomorphic features; unstable multi-thread braided channels in the unconfined valley setting; and the selection of representative monitoring sites.
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Nanocomposites of carbon nanomaterials and metallophthalocyanines : applications towards electrocatalysis
- Authors: Nyoni, Stephen
- Date: 2016
- Subjects: Nanocomposites (Materials) , Nanostructured materials , Electrocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4561 , http://hdl.handle.net/10962/d1020846
- Description: Nanohybrid materials have been prepared and examined for their electrocatalytic activity. The nanocomposites have been prepared from carbon nanomaterials (multiwalled carbon nanotubes (MWCNTs) and graphene nanosheets), cadmium selenide quantum dots and metallophthalocyanines (MPcs). The MPcs used in this work are cobalt tetraamino-phthalocyanine (CoTAPc) and tetra (4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt (II)) (CoPyPc). Their activity has also been explored in different forms; polymeric MPcs, iodine doped MPcs and covalently linked MPcs. The premixed drop-dry, sequential drop-dry and electropolymerisation electrode modification techniques were used to prepare nanocomposite catalysts on the glassy carbon electrode (GCE) surface. The sequential drop dry technique for MPc and MWCNTs gave better catalytic responses in terms of limit of detection, catalytic and electron transfer rate constants relative to the premixed. MWCNTs and CdSe-QDs have been used as intercalating agents to reduce restacking of graphene nanosheets during nanocomposite preparation. Voltammetry, chronoamperometry, scanning electrochemical microscopy and electrochemical impedance spectroscopy methods are used for electrochemical characterization modified GCE. X-ray photoelectron spectroscopy, X-ray diffractometry, transmission electron microscopy, scanning electron microscopy, infra-red spectroscopy, Raman spectroscopy were used to explore surface functionalities, morphology and topography of the nanocomposites. Electrocatalytic activity and possible applications of the modified electrodes were tested using oxygen reduction reaction, l-cysteine oxidation and paraquat reduction. Activity of nanocomposites was found superior over individual nanomaterials in these applications.
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Nascent Desires: Gendered Sexualities in Life Orientation Sexuality Education Programmes and Popular Music
- Authors: Moodley, Dale Dhersen
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3274 , http://hdl.handle.net/10962/d1021260
- Description: Formal school-based sexuality education is one medium, amongst others, that recognises young people’s sexuality, but usually as at-risk and/or risk taking subjects, or as innocent subjects. I analyse the gendered sexualities of young people as represented in: Grade 10 Life Orientation sexuality education programmes and popular music, as two mediums of sexual socialisation in Grade 10 learners’ lives, and as engaged with by Grade 10 learners and educators. I collected data from two schools in the Eastern Cape that included: (i) sections on sexuality from two Life Orientation manuals used by educators in classrooms: ‘Oxford Successful Life Orientation’ (2011), and ‘Shuters Top Class Life Orientation’ (2011); (ii) videos and lyrics of three songs voted most popular by learners which were ‘Climax’ by Usher, ‘Beez in the Trap’ by Nicki Minaj, and ‘Where Have You Been’ by Rihanna; (iii) observations of seven sexuality education classes; and, (iv) in-depth semistructured interviews conducted with eight learners and two educators. I draw on an integrated theoretical and methodological approach – Foucauldian, feminist poststructural and psychosocial psychoanalytic perspectives – to conceptualise and analyse gendered sexualities in terms of: (i) the dominant gendered discourses found in sexuality education manuals, and music videos and lyrics; (ii) the reflexive and interactive gendered subject positions taken up and/or resisted by learners and educators during classroom lessons and one-on-one interviews; and, (iii) learners’ and educators’ conscious and unconscious investments in particular gendered subject positions during one-on-one interviews. These three sets of analysis produced four major themes. The first theme centres on responsible sexuality; young women are expected to assume more sexual responsility than young men, thus curbing their sexual agency. The second theme outlines three types of pleasure – sexual, romantic and dating and/or relationship pleasure – that accord young men and women active and passive ways of exercising pleasure. The third theme highlights the heteronormative transitioning adolescent subject that constructs young women as reproductive subjects and young men as sexual subjects. The last theme focuses on gendered power relations and raunch culture, and maintains that young men are powerful and likely to commit acts of sexual violence against young women because they are powerless. The central argument developed when viewing all the themes is that dominant gendered discourse, gendered subject positions, and conscious and unconscious investments in these positions challenge the extent to which the gendered meanings that underpin adolescent learners’ sexuality are stable and fixed. The gendered discourses in the Life Orientation sexuality education programmes showed that gender is expressed rigidly, thus privileging masculine over feminine sexuality. However, the gendered discourses in the popular music contested rigid gender binaries and produced fluid and equitable masculine and feminine sexualities. The classroom practices depicted multiple and more equatable gendered sexualities, highlighting just how contested gender is. Finally, educator and learners’ personal biographies illustrated how conflicting masculine and feminine sexualities present a signficant source of emotional conflict for them. It may benefit policymakers and stakeholders to consider informal mediums of sexual socialisation for learners, such as music, when drafting the Life Orientation sexuality education curriculum, whilst also taking into account learners and educators personal lives.
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Observational cosmology with imperfect data
- Authors: Bester, Hertzog Landman
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/463 , vital:19961
- Description: We develop a formalism suitable to infer the background geometry of a general spherically symmetric dust universe directly from data on the past lightcone. This direct observational approach makes minimal assumptions about inaccessible parts of the Universe. The non-parametric and Bayesian framework we propose provides a very direct way to test one of the most fundamental underlying assumptions of concordance cosmology viz. the Copernican principle. We present the Copernicus algorithm for this purpose. By applying the algorithm to currently available data, we demonstrate that it is not yet possible to confirm or refute the validity of the Copernican principle within the proposed framework. This is followed by an investigation which aims to determine which future data will best be able to test the Copernican principle. Our results on simulated data suggest that, besides the need to improve the current data, it will be important to identify additional model independent observables for this purpose. The main difficulty with current data is their inability to constrain the value of the cosmological constant. We show how redshift drift data could be used to infer its value with minimal assumptions about the nature of the early Universe. We also discuss some alternative applications of the algorithm.
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Perceptions and experiences of G2E e-Government workplace restructuring: The cases of Buffalo City and City of Cape Town metropolitan municipalities, South Africa
- Authors: Makwembere, Sandra
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/617 , vital:19975
- Description: Taking the cases of Buffalo City Metropolitan municipality (BCMM) and City of Cape Town Metropolitan municipality (CoCT), this thesis explores the implications of government to employee (G2E) electronic government workplace restructuring on skills transformation and workplace control as perceived by back office employees and managers from different Corporate Services departments. It aims to describe the arrangements, rationale and degree of G2E e-government at BCMM and CoCT, investigate how managers, employees and union representatives identify the workplace changes relating to skill as well as document and analyse workplace struggles linked to G2E e-government. Using labour process analysis, the impacts of G2E e-government technological change are conceptualised. The labour process concepts alert us to ways in which G2E e-government technology is applied in the context of specific public sector production relations. They explain how employees and managers experience the dynamics of skill transformation and the mechanisms of control related to G2E e-government. The consideration of the labour process contrasts predominant e-government scholarly works that focus on government websites. Further, by using case study methods, namely interviews, surveys and observations, the thesis documents the particular back office employees’ and managers’ realities of G2E e-government which are marginalised in scholarly literature. The sample of respondents were selected using purposive sampling based on the subjects’ knowledge and experience, snowball sampling following referrals and random sampling during site visits. The respondents included four managers, four employees, two shop stewards and one service provider at BCMM and 16 managers, 20 employees and four shop stewards at CoCT. The findings from BCMM and CoCT illustrate how G2E e-government workplace restructuring individualises the labour process through the kind of technologies it introduces. Moreover, they show how the restructuring facilitates electronic information, communication and operations which broaden demands on technical as well as social skills. The findings also show that the restructuring extends avenues for managerial control thereby marginalising union representivity as the workplace control systems create opportunities for systemic control by management. As the South African government adopts electronic government and makes optimistic declarations of “cost saving”, “efficiency”, “productivity” and “innovation” through egovernment, the study uncovers marginalised local government employee and manager experiences. It contributes to building new knowledge on the impacts of contemporary technological change on the local government labour process and contributes to debates around the effects of G2E e-government reforms on local government.
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Phylogenetics and historical biogeography of the Teloganodidae (Ephemeroptera)
- Authors: Pereira da Conceicoa, Lyndall Louise
- Date: 2016
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/64900 , vital:28629
- Description: The Teloganodidae are a mayfly family endemic to the southwestern Cape (South Africa), with relatives in Madagascar and Asia. Like many other aquatic invertebrates in Africa, they have been considerably understudied. Research into biodiversity and biogeography allows an understanding of the earth’s biota, producing knowledge which can be used to develop strategies to preserve and monitor this biota. Mismanagement of water systems places biodiversity of river fauna under an ever-increasing extinction threat. This investigation explores rivers in under-collected areas to determine how well teloganodids have been represented in the literature, with four genera and five species described at the onset of this study. A lectotype for Lestagella penicillata Barnard (1940) has been elected and described in detail, setting “benchmark” characters for future descriptions. Standard DNA sequencing methods provide portions of three mitochondrial genes; cytochrome oxidase subunit I (COI), small subunit ribosomal 16S RNA (16S), 12S ribosomal DNA (12S) and two nuclear genes, Histone 3 (H3) and 28S ribosomal DNA (28S) for up to 255 specimens. Fore and hind wings of 79 teloganodid adults were used to examine phylogenetic signal and evolutionary divergence using geometric morphometrics. A multi-faceted approach is used to investigate relationships between clades and the effects of deep-time climatic and landform changes which have influenced the diversity and distribution seen today. Tree (Bayesian Inference and Maximum Likelihood) and network (parsimony) phylogenies, ancestral reconstruction, historical biogeography and wingevolution of the Teloganodidae are investigated. Species tree analyses discovered 27 species and six genera. Distinct lineages are restricted to catchments, and strong phylogeographic structure was found within most genera. Southern African Teloganodidae are shown to have originated in the Cretaceous, with divergence and dispersal of lineages depended on their established locality at the time of tectonic events (uplift) and climatic changes (sea level regressions and transgressions). Geographic clines in wing-shape of Lestagella across its range imply evolutionary adaptations to specific catchment landscape and environment. A detailed analysis of biodiversity has many valuable contributions, from directing future research, understanding adaptive processes, fine-tuning phylogeographical and evolutionary hypotheses, to improving management and conservation decisions in order to preserve endemic biodiversity hotspots.
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Phylogenetics of the keratin-feeding beetle family Trogidae (Coleoptera: Scarabaeoidea)
- Authors: Strümpher, Werner Petrus
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/1232 , vital:20037
- Description: Trogidae constitute a monophyletic and biologically unique family within the Scarabaeoidea, being the only keratinophagous group in its superfamily. Traditionally, the family has been divided into three distinctive genera, Omorgus Erichson, Polynoncus Burmeister, and Trox Fabricius. Although the taxonomy of the group is relatively well studied, recently changes to the existing classification have been proposed without the family as currently constituted being subjected to phylogenetic analyses. In this study I present the first molecular phylogeny for this cosmopolitan family, based on three partially sequenced gene regions: 16SrRNA, 18S rRNA and 28S rRNA domain 2. Analyses resolved relationships between and within genera and subgenera that are largely congruent with existing taxonomic hypotheses based on morphology. I recovered four well-supported radiations: Polynoncus, Omorgus, Holarctic Trox and Afrotropical Phoberus. One of the more surprising results was the monophyly of Phoberus. Based on the evidence, I propose reinstating the genus Phoberus to accommodate all Afrotropical (including Madagascan endemic) species. The results re-emphasise the validity of Scholtz’s (1986a) classification system for the genus Omorgusand its subgeneraand provide evidence of an African origin for Madagascan trogids. Divergence analysis was able to date the major events for the origin of extant lineages of Trogidae. The subsequent diversification of the major lineages is largely attributed to Pangaean and Gondwanan vicariance events in the Mid-Jurassic and early Late Cretaceous, respectively. The separation of the landmasses resulted in the evolution of four distinct groups: Omorgus, Polynoncus, Trox and Phoberus. The monophyletic subgenus Phoberus MacLeay is of particular interest; about one-third (14 of 40) of the species in the Afrotropical region have lost the ability to fly. To gain insights into the evolution of flightlessness in this clade, phylogenetic relationships among species were inferred using molecular sequence data. Four partial sequences of four genes (COI, 16S, 18S and 28S domain 2) were obtained for 27 species, covering all of the recognised species-groups. Estimated times of divergence were based on published mutation rates for COI. The results recovered eight monophyletic lineages, supporting the morphology-based subdivisions of the genus. Flightlessness evolved at least five times within the subgenus. There is no strong support for the re-acquisition of functional wings once they are lost. Diversification, and the present relictual distributions, in African Phoberus can be linked to climatic and geological events associated with the Miocene and Pliocene Climate Optimum in southern Africa. The evolution of flightlessness in Phoberus is consistent with the habitat stability hypothesis. All flightless species occupy refugial areas with relatively long-term environmental stability. Phoberus is a promising model group for studying evolutionary trends relating to flightlessness, speciation and biogeography. Flightlessness is a counterintuitive evolutionary development, given the many advantages of flight. To interpret the diversification in the flightless Phoberus capensis Scholtz, the phylogenetic relationships among several populations of P. capensis are investigated. Phylogenetic relationships among populations were inferred using molecular sequence data that suggested three distinct evolutionary lineages, which was also supported by morphological characters. Divergence time estimates suggest a Pliocene-Pleistocene diversification. Based on these results, it is suggested that P. capensis experienced climatically-driven allopatric speciation with sheltered Afrotemperate forests and high mountain peaks serving as important refugia in response to climatic exacerbations. The P. capensis complex thus represents a speciation process in which flight-restricted populations evolved in close allopatry, possibly as recently as the Pleistocene. Two of the three divergent and geographically distinct lineages are described as novel species. This study represents the most recent comprehensive work on the Trogidae. On the basis of this study, it is proposed that taxonomic changes to the generic classification of the family be made. Trogidae are formally divided into two subfamilies, Omorginae and Troginae. The subgenus Phoberus is restored to genus rank to include all the Afrotropical species, and Afromorgus is confirmed at subgeneric rank. The genus Madagatrox is synonymised with Phoberus.
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Predators of aerial insects and riparian cross-boundary trophic dynamics: web-building spiders, dragonflies and damselflies
- Authors: Chari, Lenin Dzibakwe
- Date: 2016
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/55791 , vital:26734
- Description: This thesis characterises the cross-boundary trophic interactions of a relatively small model ecosystem, the Kowie River (Eastern Cape of South Africa), to explore their epistemic implications for systems ecology. Using web-building spiders and odonates (dragonflies and damselflies) as model organisms, I sought to investigate whether the diets of predators of aerial insects could be used to assess the strength of the trophic connectivity between freshwater and terrestrial systems in relation to variables such as stream width, distance from the river and aquatic insect emergence rates and abundances. Predator diet composition was determined by using a combination of diet analysis tools: direct observations of cross-subsidies, naturally-abundant stable (carbon and nitrogen) isotope analysis and fatty acid analysis. I also sought to reveal feeding niches and guilds among riparian aerial predators and investigate how the environment influenced predators’ access to aquatic prey subsidies. As emergent aquatic insect abundances decreased with an increase in distance from the river, and increased with stream width and seasonal changes from winter to summer, stable isotope and fatty acid analyses revealed distinct changes in web-building spider diet composition. Examination of the fatty acid eicosapentaenoic acid, a component commonly used as an indicator of consumer reliance on aquatic nutritional subsidies, showed that aquatic subsidies extended further inland at the wider sections of the river. Spiders and odonates at the wider sections of the Kowie River generally received more subsidies (56 – 70%) than those at the narrower sections (25 – 60%). When terrestrial insect biomass was distinctly low in winter, the benefit of aquatic subsidisation to spiders was relatively lower at the narrower sections of the Kowie River relative to the wide sections. As such, riparian areas adjacent to wide parts of the river were more likely to support larger populations of aerial predators than those at the narrow sections. Apart from the diet changes across time and space, there was evidence of inter-specific niche partitioning in both spiders and odonates, but no differences were observed between males and females of the same species. Results showed odonates of different sizes and hunting strategies had separate dietary niches, hence varied access to aquatic nutritional subsidies. The larger odonate taxa that frequently foraged mid-air had more varied diets and relied less on aquatic emergent insects than the smaller odonates that foraged from perches near the river. There was also evidence of niche partitioning amongst the spiders, as those that built horizontal webs captured more aquatic insects (40 – 78%) than the vertical orb-web builders (20 – 66%). This study showed that the nature and extent of trophic cross-boundary linkages in riparian areas largely depended on the availability of subsidies that varied seasonally and spatially. The width of the stream and seasonal variability emerged as important predictors of emergent insect abundances/biomasses that influenced predator feeding niches. The high mobility of odonates made their reliance on aquatic nutritional subsidies different from the less mobile spiders. The link between the width of the river and the extent of trophic connectivity has implications for riparian area management and definition of riparian buffer zones. However, the variation in diet niches amongst terrestrial consumers makes the results area-specific, and more studies are required that incorporate additional terrestrial predators in other fluvial systems so that we can make some generalizations on the dynamics of riparian trophic cross-boundary links.
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Rural livelihood strategies of female headed households in former Bantustans of post-apartheid South Africa: The case of Cala, Eastern Cape Province.
- Authors: Chirau, Takunda John
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3410 , http://hdl.handle.net/10962/d1021301
- Description: Communal areas in contemporary South Africa (that is, the former Bantustans of apartheid South Africa) continue to bear and endure, albeit in new forms, socio-economic and political vulnerabilities which are negatively affecting household livelihoods. Current studies on rural livelihoods have failed to keep pace in exploring and analysing the lived experiences and ever-changing challenges faced by these rural households. This thesis provides an understanding and explanation of the livelihood activities of specifically de facto and de jure female-headed households in the former Transkei Bantustan, with a specific focus on villages in Cala. This is framed analytically by feminist theories with their emphasis on systems of patriarchy and by a rural livelihoods framework. It uses a multiplicity of research methods, including focus group discussions, in-depth interviews, life histories and survey questionnaires. The major findings of the thesis show that the female-headed households in Cala depend upon agricultural-based activities and non-agriculturally-based activities and income (including social grants) but that they exist under conditions of extreme vulnerability which are subject to fluctuation. In the end, the livelihoods of female-headed households are precarious and unstable as they live under circumstances of poverty. However, the female heads are not mere passive victims of the rural crisis in post-apartheid South Africa, as they demonstrate qualities of ingenuity and resourcefulness including through a range of coping mechanisms. At the same time, rural communities continue to be marked by patriarchal norms and practices, including systems of chieftainship, which disempower women (including female heads), though this affects de jure heads and de facto heads differently. The thesis contributes to an understanding of rural livelihoods in communal areas (or former Bantustans) of present-day South Africa by way of ‘thick descriptions’ of the everyday lives of female heads in Cala. Further, in examining rural livelihoods, it highlights the importance of bringing to bear on the livelihoods framework a feminist perspective in pinpointing the additional livelihood burdens carried by rural women.
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Selecting and augmenting a FOSS development and deployment environment for personalized video-oriented services in a Telco context
- Authors: Shibeshi, Zelalem Sintayehu
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/943 , vital:20005
- Description: The great demand for video services on the Internet is one contributing factor that led telecom companies to search for solutions to deliver innovative video services, using the different access technologies managed by them and leveraging the capacity of enforcing Quality of Service (QoS). One part of the solution was an infrastructure that guarantees QoS for these services, in the form of the IP Multimedia Subsystem (IMS) framework. The IMS framework was developed for delivering innovative multimedia services, but IMS alone does not provide the required services. This has led to further work in the area of multimedia service architectures. One noteworthy architecture is IPTV. IPTV is more than what its name implies, as it allows the development of various innovative video-oriented services and not just tv. When IPTV was introduced, many thought that it would bring back the revenue loss that telecom companies experienced to over-the-top (OTT) service providers. However, despite all its promises, the IPTV implementation has not shown as wide an uptake as one would expect. Although there could be various reasons for the slow penetration of IPTV, one reason could be the technical challenge that IPTV poses to service developers. One of the main reasons for the embarking of the research reported in this thesis was to identify and select free and open source software (FOSS) based platforms and augment them for easy development and deployment of video-oriented services. The thesis motivated how the IPTV architecture, with some modification, can be a good architecture to develop innovative video-oriented services. For a better understanding and investigate the issues of video-oriented service development on different platforms, we followed an incremental and iterative prototyping method. As a result, various video-oriented services were first developed and implementation-related issues were analyzed. This has helped us to identify problems that service developers face, including the requirement to utilize a number of protocols to develop an IPTV-based video-oriented service and the lack of a platform that provides a consistent programming interface to implement them all. The process also helped us to identify new uses cases through the process. As part of our selection process, we found that the Mobicents service development platform can be used as the basis for a good service development and deployment environment for video-oriented services. Mobicents is a Java-based service delivery platform for quick development, deployment and management of next generation network applications. Mobicents is a good choice because it provides a consistent programming interface and supports the various protocols needed in a consistent manner or an easy way to include the support for them. We used Mobicents to compose the environment that developers can use to build video-oriented services. Specifically we developed components and service building blocks that service developer can use to develop various innovative video-oriented services. During our research, we also identified various issues with regard to support from streaming servers in general and open source streaming servers in particular and also with the protocol they use. Specifically, we identified issues with Real Time Streaming Protocol (RTSP), a protocol specified as the media control protocol in the IPTV specification, and made proposals for solving them. We developed an RSTP proxy to augment the features lacking in the current streaming servers and implemented some of the features we proposed in it.
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Shifting identities: An exploration of the possibilities for a syncretic Afrikaans theatre by means of three case studies – Hex (2003), Lady Anne (2007), Ekspedisies (2008)
- Authors: Gehring, Heike
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2165 , http://hdl.handle.net/10962/d1021269
- Description: This thesis investigates the possibilities for syncretic Afrikaans language theatre within a post-1994 South African society. The research sets out to explore in what manner theatre can be language-specific, while at the same time being able to cross language contexts. This exploration is driven by the wish to develop strategies for creating Afrikaans theatre that is able to reflect on a society “united in diversity”. In this regard it is argued that for theatre to be able to both retain and cross language barriers, processes of bonding and bridging are necessary. The thesis sets out first to explain why these processes are required and then to suggest ways in which such processes can be implemented in practice. A triangular approach is used, in which conceptual and theoretical frameworks are developed to reflect on actual theatre practices. Three of my own productions are used as case studies, namely Hex (2000; 2003), Lady Anne (2007) and Ekspedisies (2008). These productions can be understood to be “boundary objects” in Henk Borgdorff’s (2012: 177) sense of the word, in that they fulfil a dual function: they are artistic productions that can also be reconstituted to serve a research purpose beyond the productions themselves. All three works were first created for public consumption before becoming cases for this thesis. Many of the strategies that were developed and tested in creating these productions are examples of ways in which bonding and bridging in Afrikaans language theatre can be understood. Chapter One of the thesis contextualises the political currents and events that necessitated the impulse towards “bonding and bridging”. In this case the political and ethical impetus behind the practical explorations has been related predominantly to the democratisation of South African society, in which a paradigm shift happened from viewing the Afrikaans language as one over many to one amongst many. Within a multilingual South Africa, concerns are raised about ways in which to create theatre in South African languages other than English (often understood to be the only possible bridging language) that are able to cross language divides. Following this introduction to language-related concerns, Chapter Two explains how the shift from apartheid to democracy made space for shifts in identity – on personal as well as institutional levels: a progression from essentialised notions of culture to the celebration of plurality. This progression is then related to theatre, with an explanation of how the post-1994 theatre landscape demanded a reimagining of the form and function of theatre. In this re-imagination the notion of a “third space” is important; something that is introduced in this chapter as an alternative to polarised identity constructions. The function of the “third space” as an in-between space and a meeting point for diverse people and entities is a strong underlying theme of this thesis and it serves as a reoccurring touchstone to the ideas put forward. Chapter Three discusses the South African arts festival culture and its contribution to the South African theatre landscape. Particular focus is placed on the Klein Karoo National Arts festival (KKNK) as a platform for the development of the Afrikaans language within a post-1994 context. What is emphasized in particular is the attempt by the KKNK festival to be linguistically and culturally exploratory and inclusive in the face of language protectionism. After the contextual background of the first three chapters, the thesis shifts to an analysis of theories related to “hybridity” and “syncretism”. In Chapter Four the argument is put forward that of the various inclusive performance and theatre models that represent a multicultural society, the most responsive forms are those that are syncretic and hybrid. Principles that can contribute to the unification and merging of diverse and polarized societal groups are described, and suggestions are made for possible ways to bring about bonding and bridging within cultural practices. Having introduced these principles, examples are offered of how these theories might be understood in other disciplines, namely, religious studies, anthropology, history and a range of cultural practices. Following this broad discussion, Chapter Five describes syncretism and hybridity more specifically in theatre by means of relevant examples. Taking the discussion further into the realm of application, Chapter Six offers an overview of “workshop theatre”, “translation” and “collage making” as strategies for putting theories of hybridity and syncretism into practice. This is followed (in Chapters Seven, Eight and Nine) by a discussion of the three productions (Hex, Lady Anne and Ekspedisies) as case studies that demonstrate how these theories can be understood in practice. Practical strategies for bridging language divides are foregrounded, such as code switching as an approach for enabling a “co-habitation” of languages; physical theatre as a means for crossing language divides; and the creation of more than one language version of a production as a tactic to accommodate shifting contexts. Following on from the discoveries made in the foregoing chapters, I conclude that theories and practices related to notions of “third space”, “hybridity” and “syncretism” are ideal for creating theatre forms (in the Afrikaans language in particular) that can truly reflect a South African society which is “united in diversity”. The thesis ends by offering suggestions for ways in which new, future identities, can be developed.
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Structural bioinformatics studies and tool development related to drug discovery
- Authors: Hatherley, Rowan
- Date: 2016
- Subjects: Structural bioinformatics , Drug development , Natural products -- Databases , Natural products -- Biotechnology , Sequence alignment (Bioinformatics) , Malaria -- Chemotherapy , Heat shock proteins , Plasmodium falciparum
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4164 , http://hdl.handle.net/10962/d1020021
- Description: This thesis is divided into two distinct sections which can be combined under the broad umbrella of structural bioinformatics studies related to drug discovery. The first section involves the establishment of an online South African natural products database. Natural products (NPs) are chemical entities synthesised in nature and are unrivalled in their structural complexity, chemical diversity, and biological specificity, which has long made them crucial to the drug discovery process. South Africa is rich in both plant and marine biodiversity and a great deal of research has gone into isolating compounds from organisms found in this country. However, there is no official database containing this information, making it difficult to access for research purposes. This information was extracted manually from literature to create a database of South African natural products. In order to make the information accessible to the general research community, a website, named “SANCDB”, was built to enable compounds to be quickly and easily searched for and downloaded in a number of different chemical formats. The content of the database was assessed and compared to other established natural product databases. Currently, SANCDB is the only database of natural products in Africa with an online interface. The second section of the thesis was aimed at performing structural characterisation of proteins with the potential to be targeted for antimalarial drug therapy. This looked specifically at 1) The interactions between an exported heat shock protein (Hsp) from Plasmodium falciparum (P. falciparum), PfHsp70-x and various host and exported parasite J proteins, as well as 2) The interface between PfHsp90 and the heat shock organising protein (PfHop). The PfHsp70-x:J protein study provided additional insight into how these two proteins potentially interact. Analysis of the PfHsp90:PfHop also provided a structural insight into the interaction interface between these two proteins and identified residues that could be targeted due to their contribution to the stability of the Hsp90:Hop binding complex and differences between parasite and human proteins. These studies inspired the development of a homology modelling tool, which can be used to assist researchers with homology modelling, while providing them with step-by-step control over the entire process. This thesis presents the establishment of a South African NP database and the development of a homology modelling tool, inspired by protein structural studies. When combined, these two applications have the potential to contribute greatly towards in silico drug discovery research.
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Synthesis and biological evaluation of novel thiazole-based compounds
- Authors: Olawode, Emmanual Oladayo
- Date: 2016
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/62955 , vital:28325
- Description: Thesis embargoed for one-year period. Expected date of release: April 2019
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Synthesis and exploration of resorcinol derivatives as Plasmodium falciparum Hsp90 inhibitors
- Authors: Umumararungu, Théoneste
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/717 , vital:19984
- Description: In this research project, we have synthesized a series of nine dimethyl ether resorcinol analogues of NMS-E973 (L-1) 38, a potent Hsp90 inhibitor. These analogues were chosen because they share the same pharmacophore with NMS-E973 (L-1) 38 and were thus expected to have a similar biological activity. Moreover, it is generally easier to synthesize the dimethyl ether resorcinol analogues of NMS-E973 (L-1) 38 as compared to their demethylated counterparts. Since other Hsp90 inhibitors such as geldanamycin 19 have demonstrated anti-plasmodial activity, we also expected our compounds to be Hsp90 inhibitors and to possess anti-plasmodial activity. However, our compounds were tested for growth inhibitory activity of Plasmodium falciparum and not for P. falciparum Hsp90 (PfHSP90) inhibitory activity. The synthesis involved a series of steps that led to the formation of the ester compound TU-011 (L-7) 43 that was then used as a precursor for different NMS-E973 (L-1) 38 analogues. The choice of analogues to be synthesized was dictated by binding affinity predictions obtained from molecular docking. The chosen synthetic analogues were active against chloroquine-sensitive Plasmodium falciparum (3D7 strain) in a Plasmodium lactate dehydrogenase assay and they were not generally cytotoxic to human cervical adenocarcinoma cell line HeLa. The most active of our compounds was TU-018 (L-103) 50 with an IC50 value of approximately 1.830 µM as compared to the standard, chloroquine, with an IC50 value of 0.01062 µM. Some of the compounds showed mild cytotoxicity towards HeLa cells with IC50 values higher than 25 µM as compared to the standard apoptosis inducer drug, emetine that had an IC50 value of 0.09948 µM. These results highlight the fact that the synthesized analogues are novel relatively non-toxic anti-plasmodial agents.
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Synthesis of chiral ketopinic acid-derived catalysts and their evaluation in asymmetric transformations
- Authors: Hassan, Yusuf
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/550 , vital:19969
- Description: Four new (+)-ketopinic acid-derived Mn(III) complexes, three of which possess pseudo C2- symmetry, were synthesised as chiral catalyst candidates. The ligands were prepared by refluxing (+)-ketopinic acid with ethane-1,2-diamine, the resolved (R,R)- and (S,S)-1,2-diaminocyclohexanes, and 1,2-diaminobenzene in chloroform. Treatment of the ligands with manganese(II) acetate tetrahydrate in refluxing ethanol afforded the respective complexes as brown amorphous powders. Characterisation of the ligands and the corresponding complexes was achieved using 1-D and 2-D NMR, IR spectroscopy, and elemental analysis. Various homogeneous asymmetric transformations, were investigated using these four complexes, viz., aldol, and Baylis-Hillman reactions, aza-Michael addition of piperidine to the Baylis-Hillman adducts, epoxidation, and ketone and imine reduction. Asymmetric aldol reactions of benzaldehyde with the aryl ketones, acetophenone, propiophenone, -tetralone, 4-nitroacetophenone, and 4-methoxyacetophenone, conducted in the presence of 10 mole % of the chiral catalysts, afforded enantioselectivities of up to 99% e.e. Asymmetric Baylis-Hillman reactions of methyl- and tert-butyl acrylates with pyridine-2- carbaldehyde, 6-methylpyridine-2-carbaldehyde, 5-chlorosalicylaldehyde, benzaldehyde, 4-chlorobenzaldehyde, and 2-nitrobenzaldehyde were conducted in the presence of catalyst 139 (10 mole %) to afford enantioselectivities of up to 44% e.e. Aza-Michael addition of piperidine to racemic Baylis- Hillman adducts in the presence of the catalyst 139 (10 mole %) was found to proceed with diastereoselectivities of up to 91% d.e. Asymmetric epoxidation of trans-methyl styrene, styrene, trans-stilbene, cis-stilbene, and indene, using a 5 mole % chiral catalyst loading and m-CPBA as the oxygen source, gave enantioselectivities of up to 32 % e.e. Asymmetric reductions of acetophenone, 3-chloropropiophenone, 4-hydroxyacetophenone, -tetralone, and 2-hydroxy-1-acetonapthone were investigated using NaBH4 as the reducing agent and a 10 mole % loading of the chiral catalysts. A stereoselectivity of 68% e.e. was obtained in the reduction of acetophenone, but attempts to reduce the selected imines to the corresponding chiral amines proved to be unsuccessful — even in the absence of the catalysts. It thus became apparent that the catalytic version of the reaction was not feasible.
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The chemistry of Algoa Bay ascidians
- Authors: Bromley, Candice Leigh
- Date: 2016
- Subjects: Sea squirts -- South Africa -- Algoa Bay , Marine metabolites , Chemistry, Analytic , Liquid chromatography , Inductively coupled plasma mass spectrometry , Metal ions , Nucleosides , Vanadium
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4560 , http://hdl.handle.net/10962/d1020606
- Description: This thesis investigates the chemistry of 25 ascidian species collected from Algoa Bay, South Africa with a concerted focus on metal accumulation by these ascidians and the possible interaction of these metals with ascidian metabolites. Chapter 2 details the screening techniques employed to establish the presence of nitrogenous metabolites (1H- 15N HMBC), hyper-accumulated metal ions (ICP-MS) and potential metal ion/ ascidian metabolite complexes (LC-ICP-MS/ESI-MS). Unfortunately, exhaustive attempts to detect intact metal ion/ascidian metabolite complexes through the use of liquid chromatography with parallel inductively coupled plasma mass spectrometry/electrospray mass spectrometry (LC-ICPMS/ ESI-MS) were unsuccessful. However, the LC-ICP-MS/ESI-MS data obtained for the crude organic extracts of six of the Algoa Bay ascidian species, Distaplia skoogi, Aplidium monile, Aplidium sp., Didemnum sp., Leptoclindines sp. and Polycitor sp. enabled identification of a number of ten halogenated metabolites, namely the indoles 2.28-2.30, and the tyramine and tyrosine derivatives (2.31-2.33, 2.41, 2.43, 2.44 and 2.46), within the ascidian extracts. This study confirmed that LC-ICP-MS/ESI-MS is a powerful tool for the dereplication of halogenated metabolites in complex mixtures especially where these compounds are present in very small amounts. This study is also the first report of these compounds (eight of which are known) in African ascidians. Compounds 2.32 and 2.46 have not been reported before from a marine source. Compounds 2.28-2.30 and 2.33 were present in sufficient amounts in the respective ascidian extracts to allow their isolation and structure elucidation using standard spectroscopic techniques Chapter 3 explores the ability of ascidians to accumulate a wide range of metal ions at concentrations which are often orders of magnitude higher than those of the surrounding sea water. Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the total ion concentrations of 24 metals in 25 Algoa Bay ascidian species. To the best of our knowledge this is the largest and most extensive investigation of metal concentrations in a group of different ascidians occurring in the same area. Hypotheisizing that the metal ion concentrations for each ascidian specimen screened may represent a unique fingerprint for each specimen principal component analysis (PCA) was used in an attempt to establish whether there were spatial, temporal or phylogenetic relationships associated with the metal concentration fingerprints of the ascidians that formed part of this study. The PCA results showed that there were no statistically significant relationships between ascidian metal ion concentrations and either the collection year or the collection site of the ascidians. However, species from the family Didemnidae provided the clearest statistical evidence supporting a phylogenetic relationship between these ascidians and their hyperaccumulated metal ion profiles. Furthermore, these results suggested that ascidian species are indeed actively concentrating metal ions from the surrounding sea water and are not simply sinks for passively accumulated metal ions. Interestingly, the concentration of vanadium in the set of ascidians studied did not appear to correlate with any of the other metals accumulated by these ascidians suggesting that there is possibly a unique method employed for the accumulation of vanadium by ascidians. Chapter 4 investigated this possibility further after the nucleosides 4.10, 4.11, 4.13, 4.15, 4.17 and 4.40 were isolated from the vanadium accumulating ascidian Aplidium monile. Studies into the interactions between nucleosides and vanadyl are unfortunately rare and usually qualitative in nature with limited information provided about the stability or structures of the complexes formed. The vanadyl accumulating aplousobranch ascidians e.g. Aplidium monile dominated our study of Algoa Bay ascidians therefore providing us with the rationale to investigate the relatively little studied binding ability and stability of vandyl-nucleoside complexes. Potentiometric studies were conducted to determine the stability constants of complexes formed between the oxovanadium ion vanadyl (VO2+) and the commercially available nucleosides 4.10-4.14. The data afforded by this analysis clearly confirmed the complexity of the vanadyl/nucleoside complexation and suggested that guanosine (4.12) formed the most stable complex with oxovanadium ions. We were also able to establish a third protonation constant for the hydroxyl moiety in 4.12 with a logK 8.87 which has not been previously reported. Finally, Chapter 5 revisited the cytoxicity two Algoa Bay ascidians, Clavelina sp. and Atriolum marinense the extracts from which produced promising bioactivity results in previous studies against oesophageal cancer cells. The HP-20 fractionated extracts of Clavelina sp. and Atriolum marinense proved to be similalrly cytotoxic to breast cancer cells. With the exception for the 100% acetone(aq)fractions the NMR data for both species suggested that most active non polar fractions were dominated by what appeared to be structurally unremarkable fatty acid glycerides and as such were not pursued further. Purification of the 100% acetone(aq)fraction of A. marinense resulted in the isolation of a styrene trimer, 5.1, common to both ascidian extracts. The NMR simulation software WIN-DAISY was employed to confirm the structure of 5.1. Attempts to establish if 5.1 was an isolation artefact or a product of marine pollution were inconclusive
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