Electrospun nanofibers : an alternative sorbent material for solid phase extraction
- Authors: Chigome, Samuel , Samuel Chigome
- Date: 2012 , 2012-03-26
- Subjects: Nanofibers -- Research Electrospinning -- Research Sorbents -- Research Extraction (Chemistry) -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4314 , http://hdl.handle.net/10962/d1004972
- Description: The work described in the thesis seeks to lay a foundation for a better understanding of the use of electrospun nanofibers as a sorbent material. Three miniaturised electrospun nanofiber based solid phase extraction devices were fabricated. For the first two, 10 mg of electrospun polystyrene fibers were used as a sorbent bed for a micro column SPE device (8 mm bed height in a 200 μl pipette tip) and a disk (I) SPE device (5 mm 1 mm sorbent bed in a 1000 μl SPE barrel). While for the third, 4.6 mg of electrospun nylon nanofibers were used as a sorbent bed for a disk (II) SPE device, (sorbent bed consisting of 5 5 mm 350 μm stacked disks in a 500 μl SPE barrel). Corticosteroids were employed as model analytes for performance evaluation of the fabricated SPE devices. Quantitative recoveries (45.5-124.29 percent) were achieved for all SPE devices at a loading volume of 100 μl and analyte concentration of 500 ng ml-1. Three mathematical models; the Boltzmann, Weibull five parameter and the Sigmoid three parameter were employed to describe the break through profiles of each of the sorbent beds. The micro column SPE device exhibited a breakthrough volume of 1400 μl, and theoretical plates (7.98-9.1) while disk (I) SPE device exhibited 400-500 μl and 1.39-2.82 respectively. Disk (II) SPE device exhibited a breakthrough volume of 200 μl and theoretical plates 0.38-1.15. It was proposed that the formats of future electrospun nanofiber sorbent based SPE devices will be guided by mechanical strength of the polymer. The study classified electrospun polymer fibers into two as polystyrene type (relatively low mechanical strength) and nylon type (relatively high mechanical strength).
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Empirical modelling of the solar wind influence on Pc3 pulsation activity
- Authors: Lotz, Stefanus Ignatius
- Date: 2012
- Subjects: Solar wind -- Research Solar activity -- Research Stellar oscillations -- Research , Magnetospheric radio wave propagation , Interplanetary magnetic fields
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5464 , http://hdl.handle.net/10962/d1005249
- Description: Geomagnetic pulsations are ultra-low frequency (ULF) oscillations of the geomagnetic field that have been observed in the magnetosphere and on the Earth since the 1800’s. In the 1960’s in situ observations of the solar wind suggested that the source of pulsation activity must lie beyond the magnetosphere. In this work the influence of several solar wind plasma and interplanetary magnetic field (IMF) parameters on Pc3 pulsations are studied. Pc3 pulsations are a class of geomagnetic pulsations with frequency ranging between 22 and 100 mHz. A large dataset of solar wind and pulsation measurements is employed to develop two empirical models capable of predicting the Pc3 index (an indication of Pc3 intensity) at one hour and five minute time resolution, respectively. The models are based on artificial neural networks, due to their ability to model highly non-linear interactions between dependent and independent variables. A robust, iterative process is followed to find and rank the set of solar wind input parameters that optimally predict Pc3 activity. According to the parameter selection process the input parameters to the low resolution model (1 hour data) are, in order of importance, solar wind speed, a pair of time-based parameters, dynamic solar wind pressure, and the IMF orientation with respect to the Sun-Earth line (i.e. the cone angle). Input parameters to the high resolution model (5 minute data) are solar wind speed, cone angle, solar wind density and a pair of time-based parameters. Both models accurately predict Pc3 intensity from unseen solar wind data. It is observed that Pc3 activity ceases when the density in the solar wind is very low, even while other conditions are favourable for the generation and propagation of ULF waves. The influence that solar wind density has on Pc3 activity is studied by analysing six years of solar wind and Pc3 measurements at one minute resolution. It is suggested that the pause in Pc3 activity occurs due to two reasons: Firstly, the ULF waves that are generated in the region upstream of the bow shock does not grow efficiently if the solar wind density is very low; and secondly, waves that are generated cannot be convected into the magnetosphere because of the low Mach number of the solar wind plasma due to the decreased density.
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Farm level institutions in emergent communities in post fast track Zimbabwe: case of Mazowe district
- Authors: Chiweshe, Manase Kudzai
- Date: 2012
- Subjects: Land reform -- Zimbabwe -- History -- 21st century Land settlement -- Social aspects -- Zimbabwe Zimbabwe -- Social conditions -- 1980- Zimbabwe -- Economic conditions Zimbabwe -- Politics and government -- 1980-
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3308 , http://hdl.handle.net/10962/d1003096
- Description: The thesis seeks to understand how emerging communities borne out of the Fast Track Land Reform Programme in Zimbabwe have been able to ensure social cohesion and social service provision using farm level institutions. The Fast Track Programme brought together people from diverse backgrounds into new communities in the former commercial farming areas. The formation of new communities meant that, often, there were 'stranger households'living next to each other. Since 2000, these people have been involved in various processes aimed at turning clusters of homesteads into functioning communities through farm level institutions. Fast track land reform precipitated economic and political crisis in Zimbabwe characterised by a rapidly devaluating Zimbabwean dollar, enormous inflation and high unemployment figures. This economic crisis has impacted heavily on new farmers who find it increasingly difficult to afford inputs and access loans. They have formed social networks in response to these challenges, taking the form of farm level institutions such as farm committees, irrigation committees and health committees. The study uses case studies from small-scale 'A1 farmers‘ in Mazowe district which is in Mashonaland Central Province. It employs qualitative methodologies to enable a nuanced understanding of associational life in the new communities. Through focus group discussions, in-depth interviews, narratives, key informant interviews and institutional mapping the study outlines the formation, taxonomy, activities, roles, internal dynamics and social organisation of farm level institutions. The study also uses secondary data collected in 2007-08 by the Centre for Rural Development in the newly resettled areas in Mazowe. The major finding of the study is that farmers are organising in novel ways at grassroots levels to meet everyday challenges. These institutional forms however are internally weak, lacking leadership with a clear vision and they appear as if they are transitory in nature. They remain marginalised from national and global processes and isolated from critical connections to policy makers at all levels; thus A1 farmers remain voiceless and unable to have their interests addressed. Farm level institutions are at the forefront of the microeconomics of survival among these rural farmers. They are survivalist in nature and form, and this requires a major shift in focus if they are to be involved in developmental work. The institutions remain fragmented and compete amongst themselves for services from government without uniting as A1 farmers with similar interests and challenges.
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Force of habit the mystical foundations of the narcotic
- Authors: Howell, Simon Peter
- Date: 2012
- Subjects: Drug addiction -- Philosophy -- Research Drug addiction -- Political aspects -- Research Cocaine abuse -- Legal status, laws, etc. -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2784 , http://hdl.handle.net/10962/d1002994
- Description: This thesis aims to investigate and deconstruct the relationship between the narcotic, its narrative, and western modernity. To reveal the relationship, this thesis argues that it is possible to understand the philosophical, political, cultural and ethical dimensions of western modernity through the ulterior lens of the narcotic. As such, this thesis investigates western modernity's relationship to (a) cocaine as a specific narcotic, and (b) the concept of the narcotic with all its attendant connotations of addictions, illegitimacy, transgression, illegality, and so on. Accordingly, the thesis is both interpretive of the historical narrative of the narcotic of cocaine, and generative in its deconstruction of the relationship between western modernity and the concept of the narcotic. The deconstruction of this relationship ultimately reveals both prior narratives not as oppositional, but as supplementary. This has radical consequences for the manner in which we engage with narcotic use and the user - if the narcotic is supplement to the logic of western modernity, at each attempt to expel the use and user of the narcotic, rather then create difference, we self implicate ourselves in that expulsion and distance. To seek a new and more just means of dealing with the concept of the narcotic, and its use, therefore requires a new epistemological framework which can at once contemplate both narratives at the same time. To this end, the thesis suggests the use of critical complexity theory as one such methodological tool, if supplemented by the thoughts and strategies of Derridian deconstruction and Foucauldian discourse analysis.
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Hydrological uncertainty analysis and scenario-based streamflow modelling for the Congo River Basin
- Authors: Tshimanga, Raphael Muamba
- Date: 2012
- Subjects: Congo River -- Regulation Hydrological surveys -- Congo River Watershed Water resources development -- Congo River Watershed Water resources development -- Environmental aspects -- Congo River Watershed Water supply -- Congo River Watershed River engineering -- Congo River Watershed
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:6029 , http://hdl.handle.net/10962/d1006158
- Description: The effects of climate and environmental change are likely to exacerbate water stress in Africa over the next five decades. It appears obvious, therefore, that large river basins with considerable total renewable water resources will play a prominent role in regional cooperation to alleviate the pressure of water scarcity within Africa. However, managing water resources in the large river basins of Africa involves problems of data paucity, lack of technical resources and the sheer scale of the problem. These river basins are located in regions that are characterized by poverty, low levels of economic development and little food security. The rivers provide multiple goods and services that include hydro-power, water supply, fisheries, agriculture, transportation, and maintenance of aquatic ecosystems. Sustainable water resources management is a critical issue, but there is almost always insufficient data available to formulate adequate management strategies. These basins therefore represent some of the best test cases for the practical application of the science associated with the Predictions in Ungauged Basins (PUB). The thesis presents the results of a process-based hydrological modelling study in the Congo Basin. One of the primary objectives of this study was to establish a hydrological model for the whole Congo Basin, using available historical data. The secondary objective of the study was to use the model and assess the impacts of future environmental change on water resources of the Congo Basin. Given the lack of adequate data on the basin physical characteristics, the preliminary work consisted of assessing available global datasets and building a database of the basin physical characteristics. The database was used for both assessing relationships of similarities between features of physiographic settings in the basin (Chapters 3 and 4), and establishing models that adequately represent the basin hydrology (Chapters 5, 6, and 7). The representative model of the Congo Basin hydrology was then used to assess the impacts of future environmental changes on water resources availability of the Congo Basin (Chapter 8). Through assessment of the physical characteristics of the basin, relationships of similarities were used to determine homogenous regions with regard to rainfall variability, physiographic settings, and hydrological responses. The first observation that comes from this study is that these three categories of regional groups of homogenous characteristics are sensible with regards to their geographical settings, but the overlap and apparent relationships between them are weak. An explanation of this observation is that there are insufficient data, particularly associated with defining sub-surface processes, and it is possible that additional data would have assisted in the discrimination of more homogenous groups and better links between the different datasets. The model application in this study consisted of two phases: model calibration, using a manual approach, and the application of a physically-based a priori parameter estimation approach. While the first approach was designed to assess the general applicability of the model and identify major errors with regard to input data and model structure, the second approach aimed to establish an understanding of the processes and identify useful relationships between the model parameters and the variations in real hydrological processes. The second approach was also designed to quantify the sensitivity of the model outputs to the parameters of the model and to encompass information sharing between the basin physical characteristics and quantifying the parameters of the model. Collectively, the study’s findings show that these two approaches work well and are appropriate to represent the real hydrological processes of Congo Basin. The secondary objective of this study was achieved by forcing the hydrological model developed for the Congo Basin with downscaled Global Climate Model (GCMs) data in order to assess scenarios of change and future possible impacts on water resources availability within the basin. The results provide useful lessons in terms of basin-wide adaptation measures to future climates. The lessons suggest that there is a risk of developing inappropriate adaptation measures to future climate change based on large scale hydrological response, as the response at small scales shows a completely different picture from that which is based on large scale predictions. While the study has concluded that the application of the hydrological model has been successful and can be used with some degree of confidence for enhanced decision making, there remain a number of uncertainties and opportunities to improve the methods used for water resources assessment within the basin. The focus of future activities from the perspective of practical application should be on improved access to data collection to increase confidence in model predictions, on dissemination of the knowledge generated by this study, and on training in the use of the developed water resources assessment techniques.
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Identification of novel marine algal compounds with differential anti-cancer activity: towards a cancer stem-cell specific chemotherapy
- Authors: De la Mare, Jo-Anne
- Date: 2012
- Subjects: Breast -- Cancer , Stem cells -- Research , Chemotherapy , Algae -- Biotechnology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4143 , http://hdl.handle.net/10962/d1016250
- Description: Breast cancer remains the leading cause of cancer-related death in women worldwide. Furthermore, it has been demonstrated that the treatment-resistant ER-PR-HER2/neu- sub-type is more common among women of African descent, necessitating the search for novel chemotherapies for this form of the disease. The secondary metabolites produced by marine algae represent a rich source of structurally unique compounds with chemotherapeutic potential, particularly in South Africa, whose oceans allegedly host 15 % of the total number of species in the world. Indeed, a recent study reported the isolation of a range of novel compounds from South African red and brown algae of the Plocamium, Portiera and Sargassum genera which displayed cytotoxicity against oesophageal cancer cells in vitro. The molecular mechanisms mediating this toxicity were unknown, as was the effect of these and similar compounds on metastatic ER-PR-HER2/neu- breast cancer cell lines or breast cancer stem cells. The current study aimed to address these questions by screening a library of twenty-two novel marine algal compounds for the ability to inhibit MDA-MB-231 and Hs578T breast cancer cells, while having no adverse effects on non-cancerous MCF12A breast epithelial cells. While twelve of these were toxic in the micromolar range against breast cancer cells, only the polyhalogenated monoterpenes RU004 and RU007, and the tetraprenylated quinone sargaquinoic acid (SQA) were identified as hit compounds based on the criteria that their cytotoxicity was specific to breast cancer and not healthy breast cells in vitro. On the other hand, the halogenated monoterpene RU015 was found to be highly toxic to both breast cancer and non-cancerous breast cell lines, while the halogenated monoterpene stereoisomers RU017 and RU018 were non-toxic to either of these cell lines. The mode of action of RU004, RU007, RU015 and SQA, together with the previously characterized carotenoid fucoxanthin (FXN), was assessed in terms of the type of cell death induced and the effect on cell cycle distribution of these compounds. Flow cytometric analysis of the extent of Hoescht 33342 and propidium iodide staining along with PARP cleavage studies suggested that SQA induced apoptosis in MDA-MB-231 cells. On the other hand, the highly toxic compound RU015 appeared to induce necrosis as evidenced by 50 kDa PARP cleavage product in MDA-MB-231 cells. The flow cytometry profiles of MDA-MB-231 and Hst578T cells treated with the hit compounds RU004 and RU007 were suggestive of the induction of apoptosis by these compounds. Cell cycle analysis by flow cytometry with propidium iodide staining revealed that both SQA and FXN induced G0-G1 arrest together with an increase in the apoptotic sub-G0 population, which agreed with previous reports in the literature. The molecular mechanism of action of SQA and FXN were further investigated by the identification of specific signal transducer molecules involved in mediating their anti-cancer activities. SQA was found to require the activity of numerous caspases, including caspase-3, -6, -8, -9, -10 and -13, for its cytotoxicity and was demonstrated to decrease the level of the antiapoptotic protein Bcl-2. On the other hand, FXN was shown to require caspase-1, -2, -3, -9 and - 10 for its toxicity. This, together with the ability to decrease the levels of Bcl-2, pointed to the involvement of the intrinsic pathway in particular in mediating the activity of FXN. The screening of algal compounds against non-cancerous breast epithelial cells carried out in this study, together with the investigation into their mechanisms of action, represent one of the few reports in which characterization of algal metabolites goes beyond the initial cytotoxicity assays. Finally, in order to assess the potential anti-cancer stem cell activity of the marine algal compounds, a subset of these was screened using a mammosphere assay technique developed in this study. The cancer stem cell (CSC) theory proposes that cancers arise from and are maintained by a specific subpopulation of cells able to undergo asymmetric cell division and termed CSCs. These CSCs are capable of anchorage-independent growth in serum-free culture conditions, such as those in the mammosphere assay. Using this assay, the novel halogenated monoterpene stereoisomers RU017 and RU018 were demonstrated to possess putative anti- CSC activity as evidenced by their ability to completely eliminate mammosphere formation in vitro. Furthermore, since RU017 and RU018 were non-toxic to both breast cancer and healthy breast cells, it appeared that the activity of the compounds was potentially specific to the CSCs. The results require further validation, but represent the first report of selective anti-CSC activity.
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Isolation, structural characterisation and evaluation of cytotoxic activity of natural products from selected South African marine red algae
- Authors: Knott, Michael George
- Date: 2012
- Subjects: Marine algae -- South Africa , Red algae -- South Africa , Pharmaceutical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3862 , http://hdl.handle.net/10962/d1015460
- Description: The medicinal chemistry of selected marine algae indigenous to South Africa was investigated. Following the isolation and characterisation of a number of new and known compounds, the associated in vitro cytotoxic profiles of these new compounds was investigated. Plocamium maxillosum yielded two new cyclic polyhalogenated monoterpenes which were characterised as 2E-chloromethine-4E-chlorovinyl-4-methyl-5-cyclohexen-1-one (2.1) and 2Z-chloromethine-4E-chlorovinyl-4-methyl-5-cyclohexen-1-one (2.2) on the basis of one and two dimensional NMR spectroscopic data and MS analysis. These compounds were also found to have good cytotoxic activity against breast cancer cell lines. Although these compounds are based on a regular monoterpene skeleton, they represent an uncommon feature not often seen in cyclic halogenated monoterpenes from marine algae. Plocamium robertiae yielded one new cyclic polyhalogenated monoterpene identified as 4,5- dibromo-5-chloromethyl-1-chlorovinyl-2-chloro-methylcyclohexane (2.6) and one known compound called 2,4-dichloro-1-chlorovinyl-1-methylcyclohexane-5-ene or Plocamene D (2.9). Portieria hornemannii was collected from Port Edward in Natal and yielded three new compounds, namely; 3Z-1,6-dibromo-3-(bromomethylidene)-2,7-dichloro-7-methyloctane (3.1), 1E,3Z-1,6-dibromo-3-(bromomethylidene)-7-chloro-7-methyloct-1-ene (3.2), 1Z,3Z- 1,6-dibromo-3-(bromomethylidene)-7-chloro-7-methyloct-1-ene (3.3), and one known compound, namely; 3S,6R-6-bromo-3-(bromomethyl)-3,7-dichloro-7-methyloct-1-ene (3.4). Compounds 3.1 and 3.2 showed no cytotoxic activity against breast cancer cells. Another Portieria hornemannii sample was collected from Noordhoek in the Eastern Cape, it yielded one known compound referred to as 3Z-6-bromo-3-(bromomethylidene)-2,7- dichloro-7-methyloct-1-ene (3.5), as well as one new compound called portieric acid A (3.6) or 5-bromo-2-(bromomethylidene)-6-chloro-6-methylheptanoic acid. Portieric acid A showed slight cytotoxic activity and also represents a new class of compound within the genus Portieria. The isolation of secondary metabolites from the South African red alga, Laurencia glomerata, yielded two known compounds; 7-hydroxylaurene (4.9) and cis-neolaurencenyne (4.12), as well as one chamigrane related compound (4.11). Laurencia flexuosa yielded one known compound called 3Z-bromofucin (4.13). Using 1H NMR, GC and molecular systematics, a novel method for identifying different species of Laurencia was also investigated.
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Mechanistic studies of unusual Miruta-Baylis-Hillman reactions
- Authors: Nyoni, Dubekile
- Date: 2012
- Subjects: Chemical reactions Benzaldehyde Acrylonitrile Methyl acrylate Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4400 , http://hdl.handle.net/10962/d1006692
- Description: This study has focussed on the application of synthetic, kinetic and exploratory theoretical methods in elucidating the reaction mechanisms of four Morita-Baylis-Hillman (MBH) type reactions, viz, i) the reactions of the disulfide 2,2'-dithiodibenzaldehyde with various activated alkenes in the presence of DBU and Ph₃P, ii) the reactions of chromone-3-carbaldehydes with MVK, iii) the reactions of chromone-2-carbaldehydes with acrylonitrile and iv) with methyl acrylate. Attention has also been given to the origin of the observed regioselectivity in Michaelis-Arbuzov reactions of 3-(halomethyl)coumarins. Cleavage of the sulfur-sulfur bond of aryl and heteroaryl disulfides by the nitrogen nucleophile DBU has been demonstrated, and a dramatic increase in the rate of tandem MBH and disulfide cleavage reactions of 2,2'-dithiodibenzaldehyde with the activated alkenes, MVK, EVK, acrylonitrile, methyl acrylate and tert-butyl acrylate has been achieved through the use of the dual organo-catalyst system, DBU-Ph₃P – an improvement accompanied by an increase in the yields of the isolated products. Detailed NMR-based kinetic studies have been conducted on the DBU-catalysed reactions of 2,2'-dithiodibenzaldehyde with MVK and methyl acrylate, and a theoretical kinetic model has been developed and complementary computational studies using Gaussian 03, at the DFT-B3LYP/6-31G(d) level of theory have provided valuable insights into the mechanism of these complex transformations. Reactions of chromone-3-carbaldehydes with MVK to afford chromone dimers and tricyclic products have been repeated, and a novel, intermediate MBH adduct has been isolated. The mechanisms of the competing pathways have been elucidated by DFT calculations and the development of a detailed theoretical kinetic model has ensued. Unusual transformations in MBH-type reactions of chromone-2-carbaldehydes with acrylonitrile and methyl acrylate have been explored and the structures of the unexpected products have been established using 1- and 2-D NMR, HRMS and X-ray crystallographic techniques. Attention has also been given to the synthesis of 3-(halomethyl)coumarins via the MBH reaction, and their subsequent Michaelis-Arbuzov reactions with triethyl phosphite. An exploratory study of the kinetics of the phosphonation reaction has been undertaken and the regio-selectivity of nucleophilic attack at the 4- and 1'-positions in the 3-chloro- and 3-(iodomethyl)coumarins has been investigated by calculating Mulliken charges, LUMO surfaces and Fukui condensed local softness functions.
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Movement patterns, stock delineation and conservation of an overexploited fishery species, Lithognathus Lithognathus (Pisces: Sparidae)
- Authors: Bennett, Rhett Hamilton
- Date: 2012
- Subjects: Reef fishes -- Behavior , Endangered species -- South Africa , Fish stock assessment -- South Africa , Fishery management -- South Africa , Fish communities -- South Africa , Sparidae , Lithognathus , Lithognathus -- Growth
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5374 , http://hdl.handle.net/10962/d1015709
- Description: White steenbras Lithognathus lithognathus (Pisces: Sparidae) has been a major target species of numerous fisheries in South Africa, since the late 19th century. Historically, it contributed substantially to annual catches in commercial net fisheries, and became dominant in recreational shore catches in the latter half of the 20th century. However, overexploitation in both sectors resulted in severe declines in abundance. The ultimate collapse of the stock by the end of the last century, and the failure of traditional management measures to protect the species indicate that a new management approach for this species is necessary. The species was identified as a priority for research, management and conservation in a National Linefish Status Report. Despite knowledge on aspects of its biology and life history, little is known about juvenile habitat use patterns, home range dynamics and movement behaviour in estuaries. Similarly, the movement and migration of larger juveniles and adults in the marine environment are poorly understood. Furthermore, there is a complete lack of information on its genetic stock structure. Such information is essential for effective management of a fishery species. This thesis aimed to address the gaps in the understanding of white steenbras movement patterns and genetic stock structure, and provide an assessment of its current conservation status. The study adopted a multidisciplinary approach, incorporating a range of methods and drawing on available information, including published literature, unpublished reports and data from long-term monitoring programmes. Acoustic telemetry, conducted in a range of estuaries, showed high site fidelity, restricted area use, small home ranges relative to the size of the estuary, and a high level of residency within estuaries at the early juvenile life stage. Behaviour within estuaries was dominated by station-keeping, superimposed by a strong diel behaviour, presumably based on feeding and/or predator avoidance, with individuals entering the shallow littoral zone at night to feed, and seeking refuge in the deeper channel areas during the daytime. Conventional dart tagging and recapture data from four ongoing, long-term coastal fish tagging projects, spread throughout the distribution of this species, indicated high levels of residency in the surf zone at the late juvenile and sub-adult life stages. Consequently, juvenile and sub-adult white steenbras are vulnerable to localised depletion, although they can be effectively protected by suitably positioned estuarine protected areas (EPAs) and marine protected areas (MPAs), respectively. It has been hypothesized that adult white steenbras undertake large-scale coastal migrations between summer aggregation areas and winter spawning grounds. The scale of observed coastal movements was correlated with fish size (and age), with larger fish undertaking considerably longer-distance coastal movements than smaller individuals, supporting this hypothesis. Given the migratory behaviour of adults, and indications that limited spawning habitat exists, MPAs designed to protect white steenbras during the adult life stage should encompass all known spawning aggregation sites. The fishery is plagued by problems such as low compliance and low enforcement capacity, and alternative management measures, such as seasonal closure, need to be evaluated. Despite considerable conventional dart tagging effort around the coastline (5 782 fish tagged) with 292 recaptures there remains a lack of empirical evidence of fish migrating long distances (> 600 km) between aggregation and spawning areas. This uncertainty in the level of connectivity among coastal regions was addressed using mitochondrial DNA sequencing and genotyping of microsatellite repeat loci in the nuclear genome, which showed no evidence of major geographic barriers to gene flow in this species. Samples collected throughout the white steenbras core distribution showed high genetic diversity, low genetic differentiation and no evidence of isolation by distance or localised spawning. Although historically dominant in several fisheries, analysis of long-term commercial and recreational catch data for white steenbras indicated considerable declines and ultimately stock collapse. Improved catch-per-unit-effort in two large MPAs subsequent to closure confirmed that MPAs can be effective for the protection of white steenbras. However, the current MPA network encompasses a low proportion of sandy shoreline, for which white steenbras exhibits an affinity. Many MPAs do not prohibit recreational shore angling, which currently accounts for the greatest proportion of the total annual catch. Furthermore, EPAs within the juvenile distribution protect a negligible proportion of the total available surface area of estuaries – habitat on which white steenbras is wholly dependent. Despite some evidence of recent increases in abundance in estuaries and the surf zone in certain areas, white steenbras meets the criteria for “Endangered” on the IUCN Red List of Threatened Species, and for “Protected species” status on the National Environmental Management: Biodiversity Act of South Africa. The species requires improved management, with consideration for its life-history style, estuarine dependency, surf zone residency, predictable spawning migrations and its poor conservation status. The multidisciplinary approach provides valuable information towards an improved scientific basis for the management of white steenbras and a framework for research that can be adopted for other overexploited, estuarine-associated coastal fishery species.
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Nanocomposites of nickel phthalocyanines as electrocatalysts for the oxidation of chlorophenols an experimental and theoretical approach
- Authors: Khene, Mielie Samson
- Date: 2012
- Subjects: Nanocomposites (Materials) -- Research Phthalocyanines -- Research Chlorophenols -- Research Electrocatalysis -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4326 , http://hdl.handle.net/10962/d1004986
- Description: In this work the interaction between peripherally (b) substituted nickel tetrahydroxyphthalocyanines (b-NiPc(OH)4 and poly-b-Ni(O)Pc(OH)4) with 4-chlorophenol is theoretically rationalized by performing calculations at the B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and 4-chlorophenol, in order to determine the reactive sites involved when 4-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: OPGE-α-NiPc(OH)8 (OPGE = ordinary pyrolytic graphite electrode, α = nonperipheral substitution), OPGE-a-NiPc(OH)4 and OPGE-β- NiPc(OH)4 are compared with those of the polymerized counterparts: OPGE-poly-α-Ni(O)Pc(OH)8, OPGE poly-a-NiPc(OH)4 and OPGE-poly-β-NiPc(OH)4, respectively. β-NiPc(NH2)4, β-NiPc(OH)4, α-NiPc(OH)4, α-NiPc(OH)8, α-NiPc(C10H21)8 are adsorbed on singled walled carbon nanotube (SWCNT) and β-NiPc(NH2)4-SWCNT (linked to SWCNT), are used to modify glassy carbon electrode (GCE) and employed for the electro oxidation of chlorophenols. The β-NiPc(NH2)4-SWCNT gave the best current response for the oxidation of 4-chlorophenol. α-NiPc(OH)8-SWCNT and α-NiPc(C10H21)8 gave the best resistance to electrode fouling due to oxidation by product of 4-chlorophenol. The synthesis of conjugates of cadmium telluride quantum dots (CdTe-QDs) capped with thioglycolic acid and peripherally substituted nickel tetraamino phthalocyanine (β-NiPc(NH2)4) complex were also employed for the oxidation of chlorophenols. Separation of one of the diastereomers of 1, 2-subnaphthalocyanine (SubNPc) was achieved as well as separation of the enantiomers. The absorption and magnetic circular dichroism spectra, together with theoretical calculations, reveal rather small variations in the frontier molecular orbitals of the SubNPc compared to conventional subphthalocyanine (SubPc), except for the destabilization of the highest occupied molecular orbital (HOMO), which results in a characteristic absorption in the Soret band region. The chirality of SubNPc, including the cyclic dichroism (CD) signs and intensities, are discussed in detail.
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Narrating emergence in the curious terrain of academic development research: a realist perspective
- Authors: Niven, Penelope Mary
- Date: 2012
- Subjects: Education, Higher -- Aims and objectives -- South Africa Universities and colleges -- South Africa Educational change -- South Africa Black people -- Education (Higher) -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1675 , http://hdl.handle.net/10962/d1003558
- Description: This dissertation adopts a realist meta-perspective on a body of the scholar's own research papers written between 2005 and 2011, all either published or in press and offered for reference in the Appendices. The six papers represent the point of departure for the thesis; they are the phenomenon for further investigation into 'what must be the case' for the research events to have emerged as they did. One aspect of this study, therefore, is an auto ethnographic account of conducting research in the field of Academic Development within varied settings and over a given time frame. But alongside this personal history it narrates cycles in the Academic Development movement in South Africa over 30 years. Margaret Archer's Social Realist principle of analytical dualism (1995) is used to disaggregate the emergent properties within these histories and to enable an analysis of the underlying mechanisms that generated them. It refers to three social domains. Firstly, it describes the material structures - the institutional environments, policies, roles or professional conditions - in which the projects were conceived. Secondly, it identifies the cultural registers that the profession was drawing on - such as theories, beliefs or discourses. Thirdly, it draws attention to the agency of individuals and communities in the field as they independently activated or mediated these various conditioning structures and registers. So the study is a systematic examination of the parts and the people in research stories, of the complex interrelationship of structural and agential elements, and of how together they have generated particular forms of knowing and kinds of knowledge in Academic Development. Drawing from this 'history-within-a-history', the study makes some claims for 'what must be the case' for substantial knowledge to flourish in a newly emergent, hotly contested and relatively unstable field. It argues that Academic Development has few shared epistemological foundations and boundaries, and its roles and functions are shifting and diverse. It describes the tensions in the field between those who have been inclined to understand it as primarily concerned with redress or equity in the postapartheid state, and yet others who have prioritised Academic Development as an efficiency project within higher education. But there is a third discourse emanating from those in the profession who have consistently argued that neither of these approaches can succeed without drawing on stronger theoretical foundations. This study endorses the view that Academic Developers need to identify more coherent ontological and epistemological frames for their research work. This has important implications for building the kind of substantial knowledge base that could be more influential in addressing the troubled terrain of South African higher education. The study refers extensively to Lewis Carroll's Alice in Wonderland (1865) and Through the Looking-Glass (1871) and to Mervyn Peake's 1946 illustrations of these children's stories, finding in these texts powerful analogies and metaphors for principles in realist philosophy and theory, and for describing a researcher's journey towards a more assured identity in the curious field of Academic Development.
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Participatory mapping, learning and change in the context of biocultural diversity and resilience
- Authors: Ali, Million Belay
- Date: 2012
- Subjects: Biodiversity conservation -- Research -- Ethiopia Cultural pluralism -- Research -- Ethiopia Ethnopsychology -- Research -- Ethiopia Adult education -- Research -- Ethiopia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:1689 , http://hdl.handle.net/10962/d1003572
- Description: This study set out to investigate the learning and change that emerged in and through participatory mapping in the context of biocultural diversity and resilience in rural Ethiopia. It did this through examining the learning and agency emerging from three participatory mapping practices (Participatory 3 Dimensional Modelling, sketch mapping and eco-cultural calendars) using two case study sites, located in the Bale Mountains and the Foata Mountains in Ethiopia, and honing in on in-depth reflective processes in two community contexts located within the broader case study sites, namely Horo Soba, Dinsho wereda in Bale; and Telecho, in Wolmera wereda, in the Foata Mountain complex. This study tried to answer three research questions related to participatory mapping: its role in mobilizing knowledge related to biocultural landscape, its role in learning and change, and its value in building resilience. The study used qualitative case study research methodology underpinned by critical realist philosophy, and used photographic ‘cues’ to structure the reporting on the cases. It used four categories of analysis: biocultural diversity, educational processes, learning and agency, in the first instance to report on the interactions associated with the participatory mapping practices as they emerged in the two case study sites. This was followed by in-depth analysis and interpretation of participatory mapping and biocultural diversity, as well as participatory mapping and learning, with an emphasis on acquisition, meaning making and identity formation processes. The in-depth analysis drew on social and learning theory, and theory of biocultural diversity and social-ecological resilience. The study also included analysis of broader change processes that were related to and emerged from the social interactions in the mapping activities, and the resultant morphogenesis (change), showing that morphogenesis, while broadly temporal, is not linear, and involves ‘little iterative morphogenic cycles’. These insights were then used to interpret how participatory mapping may contribute to resilience building in a context where social-ecological resilience is increasingly required, such as the two case study sites, where socialecological degradation is highly visible and is occurring rapidly. The study’s contribution to new knowledge lies in relation to the role of participatory mapping in facilitating learning, agency and change which, to date, appears to be under-theorised and under-developed in the participatory mapping and environmental education literature. As such, the study findings provide in-depth insight into how participatory mapping methodologies may ‘work in the world’, in contexts such as those presented in the two cases under study. It has tried to demonstrate how participatory mapping has managed to mobilize knowledge related to biocultural diversity, facilitated the acquisition of knowledge and helped members of the community to engage in meaning making activities relevant to their biocultural landscape and renegotiate their identity within the wider community context. It has also shown that dissonance is an important dynamic in the learning process; and that morphogenesis (or change) occurs over time, but also in smaller cycles that interact at different levels; and that participatory mapping cannot, by itself mobilise significant structural change, at least in the short term. It has also shown, however, that learning and the desire for change can emerge from participatory mapping processes, and that this can be utilized to adapt to the changing socio-ecological environments, potentially contributing to longer term resilience of social-ecological systems.
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Photophysicochemical and photodynamic studies of phthalocyanines conjugated to selected drug delivery agents
- Authors: Nombona, Nolwazi
- Date: 2012
- Subjects: Phthalocyanines Photochemistry Photochemotherapy Drug delivery systems Magnesium Zinc Nanoparticles Staphylococcus aureus
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4333 , http://hdl.handle.net/10962/d1004994
- Description: This work reports on the successful synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines. The synthesis of symmetrical phthalocyanines is also reported. A selection of phthalocyanines have been conjugated, covalently linked, encapsulated or mixed with selected of drug delivery agents which include gold or silver nanoparticles, poly-L-lysine, liposomes and folic acid. The influence of delivery agent on the photophysical and photochemical properties of conjugated phthalocyanine is investigated. The studies showed that the Au nanoparticle significantly lowered the fluorescence quantum yield values of the phthalocyanines. The photodynamic activity of Zn phthalocyanine-ε-polylysine conjugates in the presence of nanoparticles towards the inactivation of Staphylococcus aureus showed high photoinactivation in the presence of silver nanoparticles. The presence of silver nanoparticels from the minimal inhibition concentration (MIC₅₀) studies showed remarkable growth inhibition for the tested conjugates even at low concentrations. The conjugate also showed no dark toxicity when evaluated using the chick choriallantoic membrane (CAM) assay. The efficiency of selected zinc phthalocyanine as photodynamic therapy (PDT) agents was investigated. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizers were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either gold nanoparticles or encapsulated in liposomes. Cell viability studies showed the optimum phototoxic effect on non-malignant cells to be 4.5 J.cm⁻². The PDT effect of the liposome bound phthalocyanine showed extensive damage of the breast cancer cells. Gold nanoparticles only showed a modest improvement in PDT activity.
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Pre-concentration of heavy metals in aqueous environments using electrospun polymer nanofiber sorbents
- Authors: Darko, Godfred
- Date: 2012
- Subjects: Heavy metals -- Absorption and adsorption -- Research Nanochemistry -- Research Polystyrene -- Research Polyamides -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4337 , http://hdl.handle.net/10962/d1004998
- Description: This thesis presents an alternative approach for pre-concentrating heavy metals in aqueous environments using electro spun polymer nanofiber sorbents. The conditions for electrospinning polyethersulfone, polystyrene, polysulfone and polyamide-6 were optimized. The morphologies and porosities of the electrospun nanofibers were studied using SEM and BET nitrogen gas adsorptions. The nanofibers had mesoporous morphologies with specific surface areas up to 58 m2/g. The electro spun nanofiber sorbents were characterized in terms of their tunability for both uptake and release of heavy metals. The usability of the sorbent was also assessed. The sorbents showed fast adsorption kinetics for heavy metals « 20 min for As, Cu, Ni and Pb) in different aqueous environments. The adsorption characteristics of the sorbents best fitted the Freundlich isotherm and followed the first order kinetics. The efficiencies of adsorption and desorption of heavy metals on both imidazolyl-functionalized polystyrene and amino-functionalized polysulfone sorbents were more than 95% up to the fifth cycle of usage. Reusability improved dramatically (up to 10 runs of usage) when mechanically stable amino-functionalized nylon-6 electro spun nanofibers were used. The capacity of the amino-functionalized nylon-6 sorbent to pre-concentrate heavy metals compared very favourably with those of aqua regia and HN03+H202 digestions especially in less complex matrices. Due to their highly porous nature, the electro spun nanofibers exhibited high adsorption capacities (up to 50 mg/g) for heavy metal ions. The loading capacities achieved with the imidazolyl-functionalized sorbent were higher than those for amino-functionalized mesoporous silica and biomass-based sorbents. The electro spun nanofiber sorbents presents an efficient and cost effective alternative for preconcentrating heavy metals in aqueous environments.
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Quality of work and work life: understanding the work ethic of medical professionals in selected hospitals in the Eastern Cape region of South Africa
- Authors: Kwizera, Alice Stella
- Date: 2012
- Subjects: Hospitals -- Medical staff -- South Africa -- Eastern Cape Work ethic -- South Africa -- Eastern Cape Medical personnel -- Job satisfaction -- South Africa -- Eastern Cape Protestant work ethic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3323 , http://hdl.handle.net/10962/d1003111
- Description: This thesis reports a study of work ethic values, beliefs and attitudes held by medical professionals in selected hospitals in the Eastern Cape, South Africa. The study was in response to the public outcry about the declining work ethic and poor service delivery in South Africa’s healthcare sector. Scholarly interest in the work ethic and its role in economic development dates back to Max Weber’s classical work, which was the starting point for my study. The German economic sociologist published his seminal essay on The Protestant Ethic and the Spirit of Capitalism in 1904/1905. Since that time, Weber’s ideas on the Protestant work ethic continue to inform and influence studies of the contemporary work ethic, which is thought to have become secularised. My study was informed by data collected in 2009 through a questionnaire survey and personal interviews. A total of 174 doctors and nurses, working in four urban, periurban and rural hospitals near East London, completed a self-administered questionnaire. The questionnaire replicated the Multi-Dimensional Work Ethic Profile (MWEP) developed by Miller, Woehr and Hudspeth in 2001/2002. The instrument examines seven critical dimensions of the work ethic, namely self-reliance, morality, (foregoing) leisure, hard work, centrality of work in life, not wasting time, and delay of gratification. In addition, I conducted personal interviews in the same four hospitals with 41 hospital managers, doctors, nurses, and patients to discuss their understanding of the work ethic and its practical application. The study found that both doctors’ and nurses’ overall work ethic scores on the MWEP scale were above average. Although there was no significant difference between the overall work ethic scores of the two professions, doctors scored significantly higher than nurses on the ‘hard work’ and ‘self reliance’ dimensions of the work ethic scale. In the qualitative study, the doctors’ work ethic was rated much more highly than the nurses’ by their superiors and patients; and the work ethic of nurses in the urban hospitals was rated much lower than that of their rural colleagues. In contradiction to the idea of the secularization of the contemporary work ethic, religiosity and religious beliefs were influential in the endorsement of work ethic principles. In line with the notion that ‘happy’ workers are more productive, job and life satisfaction were found to be strong correlates of the work ethic of medical professionals.
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Quantification of the cross-sectoral impacts of waterweeds and their control in Ghana
- Authors: Akpabey, Felix Jerry
- Date: 2012
- Subjects: Water hyacinth -- Control -- Environmental aspects -- Ghana Alien plants -- Research -- Ghana Introduced organisms Economic development -- Social aspects -- Research -- Ghana
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5748 , http://hdl.handle.net/10962/d1005435
- Description: The Akosombo Dam on the Volta River in Ghana was built in 1963 to provide cheap energy to fuel industry and to accelerate the economic growth of the country. It provides hydroelectric power, enhanced fishing and water transportation upstream, and improved opportunities for irrigated farming, especially in the lower reaches, and their attendant economic multiplier effects. A few years after the construction of this major dam, a rapid expansion of industrialization took place in Ghana. This brought about an exponential increase in demand for more electrical power. This led to the construction of a smaller dam at Akuse, downstream of the Akosomho Dam in 1981 and the formation of a headpond at Kpong. The impoundment of the river at the two sites (Akosombo and Kpong) caused an alteration in the existing ecological and biophysical processes in the river basin, including a slowing of the flow of the river, upstream and downstream. Changes in the natural processes, such as a reduction in the flow of the river and an increase in nutrient status of the water, resulted in an invasion of aquatic weeds, increasing the density of aquatic snails (intermediate hosts of schistosomiasis), silting and closure of the estuary, as well as other more subtle effects. The invasion of the river's main course and the dams by aquatic plants led to a corresponding reduction of navigable water both upstream and downstream. The aim of this thesis was to quantify the impact and control of waterweeds, especially water hyacinth, Eichhornia crassipes (Mart) Solms-Laubach (Pontederiaceae), in Ghana. A floral survey on the Kpong Headpond recorded 49 emergent, 12 free floating and I submerged aquatic plant species, many of which were indigenous, but the exotic or introduced water hyacinth was recorded at most of the sampling sites, and was the most abundant and had the biggest impact on the utilization of the water resource. Mats of water hyacinth served as substrates for other, indigenous species to grow out into the main channel of the headpond, including the intake point of the Kpong head works of the Ghana Water Company Limited (GWCL) and landing sites for boats. These mats resulted in a reduction of the fish (fin and shell) harvest, reducing the annual production to far below demand. Water hyacinth was also shown to have severe health implications. A survey of the Ministry of Health records showed that the prevalence of both urinary and intestinal schistosomiasis had risen significantly over time as the abundance of waterweeds, most notably water hyacinth, increased, and ranged between 70% and 75% but up to 100% in some lakeside communities. Based on the work done by an NGO on board the medical boat ("Onipa Nua "), losses in terms of money due to the effect on health of the aquatic weed infestations on the Volta River in 2006 amounted to US$ 620,000. Economic losses due to invasive alien aquatic weeds were also calculated on the Oti River Arm of Lake Volta. It was estimated that about US$2.3 million per annum would be lost to the Volta Lake Transport Company and individual boat transport operators if this section of the river were 100% covered by aquatic weeds (water hyacinth and Salvinia molesta D.S. Mitchell (Salviniaceae)). It was also estimated that US$327,038 was spent annually in monitoring and managing the weeds in the Oti River. Control interventions for aquatic weeds have been implemented in river systems in Ghana. The biological control agents Neochetina bruchi Hustache (Coleoptera, Curculionidae) and Neochetina eichhorniae Warner (Coleoptera, Curculionidae) have been used on water hyacinth infestations in the Oti River Arm of Lake Volta, the Tano River and the Lagoon complex in the south-western part of the country. Cyrtobagous salviniae Calder and Sands (Coleoptera: Curculionidae) has been used to control salvinia, and Neohydronomous affinis Hustache (Coleoptera: Curculionidae) to control water lettuce, Pistia stratiotes Lilmaeus (Araceae) in the Tano River and Lagoon complex. Although these projects have been regarded as successful, they have relied on research from elsewhere in the world and no postrelease quantification has been conducted. In evaluating the impact of the biological control agents Neochetina bruchi and Neochetina eichhorniae weevils on water hyacinth infestations in the Tano River, fresh adult feeding scars were recorded as well as the numbers of adult weevils on each water hyacinth plant sampled at six sites. Despite being released in 1994, weevil numbers and resultant damage to plants in the Tano Lagoon was low in comparison to other regions of the world where these agents have been used. The main reason for this is that this lagoon floods seasonally, washing weevil-infested plants out to sea. Water hyacinth then re-infests the lagoon from seed and the weevil populations are low. To resolve this situation, two courses of action are proposed. The first is to mass rear the weevils along the shore of the lagoon and release them when the first seedlings recruit. The second proposal is that additional agents that have shorter lifecycies and are more mobile than the weevils should be released. To this end, the water hyacinth mirid, Eccritotarsus catarinensis (Carvalho) (Hemiptera: Miridae) was imported from South Africa and released onto the Tano Lagoon in 2009. Retrospective laboratory host specificity trials were conducted on Neachetina eichharniae and Neachetina bruchi weevils 15 years after their release into Ghana to see if any variation in their host ranges had occurred. Considerable damage was inflicted on the E. crassipes leaves by the Neachetina weevils, while little feeding damage was recorded on both Heteranthera callifalia Kunth. (Pontederiaceae) and Eichharnia natans (P.Beauv.) Solms (Pontederiaceae). All the weevils introduced on H callifalia and E. natans died after the first week. This study served to confirm the host specificity and thereby the safety of these agents. Invasive alien aquatic macrophytes have negative impacts on the environment and economy of Ghana. The control of these weeds is essential to socioeconomic development and improved human health standards in riparian communities. Biological control offers a safe and sustainable control option, but requires diligent implementation. However, aquatic weed invasion is more typically a result of the anthropogenically induced eutrophication of water bodies, and this is the main issue that has to be addressed.
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Studies on existing and new isolates of Cryptophlebia leucotreta granulovirus (CrleGV) on Thaumatotibia leucotreta populations from a range of geographic regions in South Africa
- Authors: Opoku-Debrah, John Kwadwo
- Date: 2012
- Subjects: Cryptophlebia leucotreta Cryptophlebia leucotreta -- South Africa Cryptophlebia leucotreta -- Biological control Cryptophlebia leucotreta -- Life cycles Baculoviruses Lepidoptera -- Biological control Tortricidae -- Biological control Microbial insecticides Pests -- Integrated control
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5778 , http://hdl.handle.net/10962/d1005466
- Description: Baculoviruses are arthropod-specific DNA viruses that are highly virulent to most lepidopteran insects. Their host specificity and compatibility with IPM programmes has enabled their usage as safe microbial insecticides (biopesticides). Two baculovirus-based biopesticides, Cryptogran and Cryptex, which have been formulated with Cryptophlebia leucotreta granulovirus (CrleGV) have been registered for the control of false codling moth (FCM), Thaumatotibia (=Cryptophlebia) leucotreta (Meyrick) (Lepidoptera: Tortricidae) in South Africa and have been successfully incorporated into IPM programmes. However, several studies have indicated that insects can develop resistance to baculovirus-based biopesticide as was shown with field populations of codling moth (CM), Cydia pomonella (L.), which developed resistance to the biopesticide Cydia pomonella granulovirus (CpGV-M) in Europe. Other studies have shown that, under laboratory conditions, FCM populations differ in their susceptibility to Cryptogran and Cryptex. In order to investigate difference in susceptibility as well as protect against any future resistance by FCM to Cryptogran and Cryptex, a search for novel CrleGV-SA isolates from diseased insects from different geographic regions in South Africa was performed. Six geographic populations (Addo, Citrusdal, Marble Hall, Nelspruit, Baths and Mixed colonies) of FCM were established and maintained in the laboratory. Studies on the comparative biological performance based on pupal mass, female fecundity, egg hatch, pupal survival, adult eclosion and duration of life cycle of the Addo, Citrusdal, Marble Hall, Nelspruit and Mixed colonies revealed a low biological performance for the Citrusdal colony. This was attributed to the fact that FCM populations found in the Citrusdal area are not indigenous and may have been introduced from a very limited gene pool from another region. When insects from five colonies, excluding the Baths colony, were subjected to stress by overcrowding , a latent baculovirus resident in the Addo, Nelspruit, Citrusdal, Marble Hall and Mixed colonies was brought into an overt lethal state. Transmission electron micrographs revealed the presence of GV occlusion bodies (OBs) in diseased insects. DNA profiles obtained by single restriction endonuclease analysis of viral genomic DNA using BamH 1, Sa/1, Xba1 , Pst1, Xh01 , Kpn1, Hindlll and EcoR1 revealed five CrleGV-SA isolates latent within the insect populations. The new isolates were named CrleGV-SA Ado, CrleGV-SA Cit, CrleGV-SA Mbl, CrleGVSA Nels and CrleGV-SA Mix isolates. The novelty of the five CrleGV-SA isolates was confirmed by the presence of unique submolar bands, indicating that each isolate was genetically different. PCR amplification and sequencing of the granulin and egt genes from the five isolates revealed several single nucleotide polymorph isms (SNPs) which, in some cases, resulted in amino acid substitutions. DNA profiles from RFLPs, as well as phylogenetic analysis based on granulin and egt sequencing showed the presence of two CrleGV-SA genome types for the CrleGV-SA isolate. Cryptex and CrleGV-SA Ado, CrleGV-SA Cit, CrleGV-SA Mbl and CrleGV-SA Mix were placed as members of Group one CrleGV-SA, and Cryptogran and CrleGV-SA Nels isolate were placed into Group two CrleGV-SA. In droplet feeding bioassays, the median survival time (STso) for neonate larvae inoculated with Group one and two CrleGV-SA were determined to range from 80 - 88 hours (3.33 - 3.67 days), for all five colonies. LDso values for Group one and two CrleGV-SA against neonates from the Addo, Citrusdal, Marble Hall, Nelspruit and Mixed colonies varied between some populations and ranged from 0.80 - 3.12 OBs per larva, indicating some level of variation in host susceptibility. This is the first study reporting the existence of genetically distinct CrleGV baculovirus isolates infecting FCM in different geographical areas of South Africa. The results of this study have broad-ranging implications for our understanding of baculovirus-host interactions and for the application of baculovirus basedbiopesticides.
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Synthesis, characterization and antimicrobial activity of copper (II) complexes of some hydroxybenzaldimines and their derivatives
- Authors: Sobola, Abdullahi Owolabi
- Date: 2012
- Subjects: Copper , Schiff bases , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4534 , http://hdl.handle.net/10962/d1016258
- Description: This study focuses on the antimicrobial activity of Cu(II) complexes of some orthohydroxybenzaldimines and its derivatives. Four different categories of Schiff base ligands were prepared by condensing salicylaldehyde, o-vanillin, p-vanillin and vanillin with p- and osubstituted anilines; 1-aminonaphthalene; 2- and 3-aminopyridine; 2- and 3- aminomethylpyridine as well as 2-aminobenzimidazole. The last category was prepared from ophenylenediamine and o-vanillin. The Schiff base ligands have been characterized by a combination of elemental analysis and spectral (¹H- and ¹³C-NMR, UV/Visible, infrared and Raman) data. The existence of strong intramolecular hydrogen bonding in the orthohydoxybenzaldimines was evident from the chemical shift values of the hydroxyl proton in the ¹H-NMR spectra of the Schiff base ligands. The hydroxyl proton resonates at high frequency and thus absorbed far downfield at 13.46-11.83 ppm, reflecting the presence of hydrogen bonding between the hydroxyl proton and the imine nitrogen. In the p-substituted aniline analogues of the Schiff base, a plot of the chemical shift values of the hydroxyl proton against the Hammett's substituent parameters gave a linear correlation between the electronegativities of the substituents and the chemical shift values. The nitro group with the highest electronegativity caused the least deshielding of the hydroxyl proton and thus absorbed upfield compared to the less electronegative substituents such as the CH3 and OCH3 analogues. Likewise, in the solid state infrared spectra of the ligands, the hydroxyl stretching band of the ortho-hydroxyl Schiff base ligands was observed as a very broad band and at much lower frequency, 3100-2100 cm⁻¹, indicating the existence of strong intramolecular hydrogen bonding. In the same vein, ¹H- and ¹³C-NMR spectral data for the Schiff base ligands indicated that the prepared compounds exist in the enol form in aprotic solvent, chloroform. The methine proton appeared as singlet and there was no carbonyl signal in the ¹³C-NMR spectra of the Schiff base ligands. This was supported by the infrared data having no vibrational band attributable to the carbonyl stretching of the keto-form of the Schiff base ligands in solid state. However, the UV/Visible study of the Schiff base ligands in protic solvent, methanol, suggested the existence of some of the Schiff base ligands in keto-enol form. A band at greater than 400 nm was observed in the UV/Visible spectra of the ligands and this has been attributed to the presence of the keto form of orthohydroxyl Schiff base ligands in solution. A plot of the molar absorptivity (ε) of the band at greater than 400 nm against Hammett substituent parameters revealed that the intensity of the bands increased with the electronegativity of the substituents. The Cu(II) complexes of salicylaldehyde, o-vanillin and a few p-vanillin based Schiff base ligands are reported in this work. It was observed that introduction of Cu(II) ions into the ligand system resulted in the hydrolysis of the imine band in few cases. All the isolated complexes have been characterized by elemental analysis, conductivity measurement, infrared and UV/Visible spectral data. The structures of three of the Cu(II) complexes were further confirmed by X-ray single crystal diffraction. The Schiff base ligands either coordinated as neutral base through the imine nitrogen or via the imine nitrogen and the phenolic oxygen atoms. In addition, the benzimidazole-based and ovan-2-pico analogues equally coordinated through the imidazole N-3 nitrogen and the azine nitrogen respectively; thus acted as tridentate. In general, the synthesized Cu(II) complexes fell into seven categories viz: [Cu(LH)Cl(H₂O)]Cl; [Cu(LH)₂Cl₂].xH₂O; [CuL₂]; [Cu₂L₂]; [Cu(LH)Cl(H₂O)]Cl; and [MLCl]. The Cu(II) complexes of the form, M(LH)₂Cl₂.xH₂O were either 1:1 or non-electrolyte in methanol and DMF. The third category, CuL₂, was however, non-electrolyte existing as neutral four coordinate Cu(II) complexes. X-ray single crystal structure of Cu(II) complexes derived from the ammonia-based Schiff bases revealed a square planar geometry for the complexes and this agreed with the planar geometry that has been reported for Cu(II) complexes of N-arylsalicylaldimines of the type studied in this work. The complexes, [Cu₂L₂], resulted from the ortho-hydroxyaniline analogues and were polymeric with the Schiff base ligands coordinating to the Cu(II) ions as tridentate dibasic via the imine nitrogen, phenolic oxygen and the aminophenolic oxygen atoms. Cu(II) complexes prepared from ovan-2-ampy and ovan-2-pico Schiff bases were of the forms [Cu(LH)Cl(H₂O)]Cl and [CuLCl] respectively. The X-ray crystal structure of [Cu(ovan-2- pico)Cl] revealed a four-coordinate square planar geometry for the complex. In the same vein, the o-phenylenediamine complexes were of the form [Cu(L)(H₂O)], with the X-ray crystal structure of [Cu(bis-ovanphen)(H₂O)] revealing a square pyramidal geometry. The Schiff base ligands and the isolated Cu(II) complexes have been evaluated for their antimicrobial activity against three bacterial strains (Escherichia coli ATCC® 8739™*, Staphylococcus aureus subsp. aureus ATCC® 6538™* and Bacillus subtilis subsp. spizizeni ATCC® 6633™*) and one fungal strain, Candida albicans ATCC® 2091™*, using agar disc diffusion and broth dilution techniques. It was observed that the presence of the methoxyl group at the ortho-position of the aldehyde moiety of the Schiff base ligands enhanced the activity of the ligand tremendously and thus the o-vanillin analogues showed the highest potency against the tested organisms. In addition, the hydroxyaniline analogues were equally the most promising of all the substituted aniline based Schiff bases. The o-vanillin analogues of the aminopyridines and aminomethylpyridines also exhibited significant activity against the tested organisms. All the 2-aminobenzimidazole series were active against the tested organisms. It should be noted that E. coli was the least susceptible of all the microorganisms while the highest potency was exhibited against the fungus of choice, Candida albicans. Lastly, chelation of the Schiff base ligands with Cu(II) ions did not have significant influence on the activity of the free ligands.
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Synthetic and bioactivity studies of antiplasmodial and antibacterial marine natural products
- Authors: Young, Ryan Mark
- Date: 2012
- Subjects: Antibacterial agents Marine natural products Marine pharmacology Plasmodium falciparum Staphylococcus aureus Isocyanides Imidazoles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4378 , http://hdl.handle.net/10962/d1005043
- Description: This thesis is divided into two parts, assessing marine and synthetic compounds active firstly against Plasmodium falciparum (Chapter 3 and 4) and secondly active against methicillin resistant Staphylococcus aureus (MRSA, Chapter 5). In Chapter 3 the synthesis of nine new tricyclic podocarpanes (3.203-3.207 and 3.209-3.212) from the diterpene (+)-manool is described. Initial SAR study of synthetic podocarpanes concluded that the most active compound was a C-13 phenyl substituted podocarpane (3.204, IC₅₀ 6.6 μM). By preparing analogues with varying halogenated substituents on the phenyl ring (3.209-3.212) the antiplasmodial activity was improved (IC₅₀ 1.4 μM), while simultaneously decreasing the haemolysis previously reported for this class of compounds. Inspired by the antiplasmodial activity of Wright and Wattanapiromsakul’s tricycle marine isonitriles (2.16-2.21 and 2.24-2.27) an unsuccessfully attempt was made to convert tertiary alcohol moieties to isonitrile functionalities in compounds 3.188, 3.204-3.207 and 3.209-3.212. Over a decade ago Wright et al. proposed a putative antiplasmodial mechanism of action for marine isonitriles (2.4, 2.9, 2.15, 2.19 and 2.35) and isothiocyanate (2.34) which involved interference in haem detoxification by P. falciparum thus inhibiting the growth of the parasite. In Chapter 4 we describe how we successfully managed to scale down Egan’s β-haematin inhibition assay for the analyses of small quantities of marine natural products as potential β-haematin inhibitors. Our modified assay revealed that the most active antiplasmodial marine isonitrile 2.9 (IC₅₀ 13 nM) showed total β-haematin inhibition while 2.15 (IC₅₀ 81 nM) and 2.19 (IC₅₀ 31 nM) showed partial inhibition at three equivalents relative to haem. Using contempary molecular modelling techniques the charge on the isonitrile functionality was more accurately describe and the modified charge data sets was used to explore docking of marine isonitriles to haem using AutoDock. In Chapter 5 we describe how a lead South African marine bisindole MRSA pyruvate kinase inhibitor (5.8) was discovered in collaboration with colleagues at the University of British Columbia (UBC) and how this discovery inspired us to design a synthetic route to the dibrominated bisindole, isobromotopsentin (5.20) in an attempt to increase the bioactivity displayed by 5.8. We devised a fast and high yielding synthetic route using microwave assited organic synthesis. We first tested this synthesis using simple aryl glyoxals (5.27-5.32) as precursors to synthesize biphenylimidazoles (5.21-5.26), which later allowed us to synthesize the ascidian natural product 5.111. This method was sucessfully extended to the synthesis of deoxytopsentin (5.33) from an N-Boc protected indole methyl ketone (5.89). We subsequently were able to effectively remove the carbamate protection via thermal decomposition by heating the protected bisindole imidazole (5.90) in a microwave reactor for 5 min under argon. The synthesis of 5.20 resulted in an inseparable mixture of monoprotected and totally deprotected topsentin products, and due to time constraints we were not able to optimise this synthesis. Nonetheless our synthesis of the marine natural product 5.33 which was faster and higher yielding than previously reported routes could be extended to the synthesis of other topsentin bisindoles (5.138-5.140). Work towards this goal continues in our laboratory.
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Systematic marine spatial planning and monitoring in a data poor environment: a case study of Algoa Bay, South Africa
- Authors: Chalmers, Russell
- Date: 2012
- Subjects: Spatial ecology -- South Africa -- Algoa Bay , Coastal zone management -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5373 , http://hdl.handle.net/10962/d1015695
- Description: Globally the failure of traditional fisheries management approaches is evident through the increasing number of overexploited or depleted marine stocks. Past sectoral management has failed to address cumulative impacts of fisheries activities on ecosystem health. Ecosystem based approaches have been advocated as a viable alternative for sustainable management of marine ecosystems as they present a holistic and precautionary approach, which integrates management of multiple activities with that of maintaining ecological health. Although conceptually advanced, implementation has been poor due to the complexities of competing ecological and socio-economic management objectives. Marine spatial planning can facilitate the implementation of ecosystem based management as it is able to address the spatial heterogeneity of biological communities and anthropogenic activities. Ecosystem based management approaches aim to address the full range of anthropogenic drivers on the marine environment, including but not limited to fisheries, tourism, coastal development, and land and marine based pollution sources amongst others. Fisheries activities have a direct impact on the local marine environment and were therefore the focus of this study which forms a starting point for implementing ecosystem based management in Algoa Bay. It is envisaged that future research will build on this foundation and include additional anthropogenic drivers into the management and monitoring strategies developed in this study in order to achieve a truly holistic ecosystem approach to management in Algoa Bay. Algoa Bay is situated centrally within the warm-temperate Agulhas bioregion along the east coast of South Africa and is the largest and best formed logarithmic spiral bay along this section of coastline. A large city, two commercial ports and several coastal settlements are located within Algoa Bay and a wide range of marine based activities occur within the area. A large section of the coastline is proclaimed as a National Park yet only two small offshore marine areas are formally protected. The development of a large marine protected area (MPA) adjoining the terrestrial section was proposed in the mid-1990s but a lack of adequate spatial data with which to quantify the fishery costs and conservation benefits led to wide scale public opposition and halted the declaration process. The primary goal of this study was to obtain and analyse baseline data to understand spatial and temporal trends in the distribution and abundance of fish populations and fisheries activities in order to develop a spatial framework for marine conservation and management in a data limited situation using Algoa Bay, South Africa as a case study. Furthermore, it aims to contribute to the development of a monitoring framework to evaluate the success of implementation and the resultant changes in biological and socio-economic environments. This information will be used to re-initiate the stakeholder engagement process in the future.
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