Prototyping a peer-to-peer session initiation protocol user agent
- Authors: Tsietsi, Mosiuoa Jeremia
- Date: 2008 , 2008-03-10
- Subjects: Computer networks , Computer network protocols -- Standards , Data transmission systems -- Standards , Peer-to-peer architecture (Computer networks) , Computer network architectures
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4646 , http://hdl.handle.net/10962/d1006603 , Computer networks , Computer network protocols -- Standards , Data transmission systems -- Standards , Peer-to-peer architecture (Computer networks) , Computer network architectures
- Description: The Session Initiation Protocol (SIP) has in recent years become a popular protocol for the exchange of text, voice and video over IP networks. This thesis proposes the use of a class of structured peer to peer protocols - commonly known as Distributed Hash Tables (DHTs) - to provide a SIP overlay with services such as end-point location management and message relay, in the absence of traditional, centralised resources such as SIP proxies and registrars. A peer-to-peer layer named OverCord, which allows the interaction with any specific DHT protocol via the use of appropriate plug-ins, was designed, implemented and tested. This layer was then incorporated into a SIP user agent distributed by NIST (National Institute of Standards and Technology, USA). The modified user agent is capable of reliably establishing text, audio and video communication with similarly modified agents (peers) as well as conventional, centralized SIP overlays.
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Purification, characterisation and application of inulinase and transferase enzymes in the production of fructose and oligosaccharides
- Authors: Mutanda, Taurai
- Date: 2008
- Subjects: Fructose Transferases Oligosaccharides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4448 , http://hdl.handle.net/10962/d1007734
- Description: Inulin hydrolysis can occur as a result of the action of exoinulinases and endoinulinases acting alone or synergistically. Exoinulinases cleave the non-reducing β-(2, I) end of inulin releasing fructose while endoinulinases act on the internal linkages randomly to release inulotrioses (F₃), inulotetraoses (F₄) and inulopentaoses (F₅) as major products. Fructosyltransferases act by cleaving a sucrose molecule and then transferring the liberated fructose molecule to an acceptor molecule such as sucrose or another oligosaccharide to elongate the short chain fructooligosaccharide. The production of high yields of oligosaccharides of specific chain length from simple raw materials such as inulin and sucrose is a challenge. Oligosaccharides of chain length up to degree of polymerisation (DP) 5 and fructose were produced using preparations of three commercial microbial enzymes. Production of these novel oligosaccharides was achieved by employing response surface methodology (RSM) with central composite experimental design (CCD) for optimising product yield. Using a crude Novozyme 960 endoinulinase preparation isolated from Aspergillus niger, the following conditions gave a high inulooligosaccharide (lOS) yield, temperature (60 ºC), 150 g/L inulin concentration, 48 h incubation; pH 6.0 and enzyme dosage of 60 U/ml. Under these conditions, inulotrioses (70.3 mM), inulotetraoses (38.8 mM), and inulopentaoses, (3.5 mM) were produced. Response surface regression predicted similar product levels under similar conditions. The crude endoinulinase was purified through a three step purification procedure with a yield of 1.11 % and 3.5 fold purification. The molecular weight of this endoinulinase was estimated to be 68 .1 kDa by SDS-PAGE and its endoinulinase nature was confirmed by native PAGE. The purified endoinulinase was more efficient in production of lOS than the crude endoinulinase preparation. The purified endoinulinase demonstrated a high affinity for the inulin substrate (Km[subscript] 3.53 mM, Vmax[subscript] 666.67 μmol/min/ml). Pectinex Ultra SP-L, a commercial crude enzyme preparation isolated from Aspergillus aculeatus is a cocktail of several enzymes including a fructosyltransferase. The crude enzyme showed both transfructosylation and hydrolytic activity in 200 to 600 g/L sucrose. The main fructooligosaccharides produced from sucrose were l-kestose (GF₂), nystose (GF₃) and fructofuranosyl nystose (GF₄). After the first RSM, with the coded independent variables of temperature, incubation time, pH and sucrose concentration, the highest levels of GF₂, was 68.61 mM, under sucrose concentration 600 g/L, temperature 60°C, enzyme dosage 20 U/ml , pH 5.6, after 4 h incubation. A sucrose concentration of 400 g/L favoured the synthesis of high levels of GF₃ and GF₄. In the second RSM the maximal yields of GF₂, GF₃ and GF₄ were 152.07 mM, 131.38 mM and 43.99 mM respectively. A purified fructosyltransferase did not synthesise GF₄. Ammonium ions were demonstrated to enhance the yield of FOS. A mixture of glucose and fructose was used as substrate for FOS synthesis and no FOS were formed. Glucose was shown to be an end product inhibitor of the fructosyltransferase and therefore hinders the formation of high FOS yield. Fructozyme, isolated from Aspergillus ficuum is a mixture of exo and endoinulinases with the former being predominant was used for fructose production from inulin hydrolysis. The exoinulinase was purified to electrophoretic homogeneity by a three step purification procedure. The molecular weight of the enzyme was estimated to be 53 kDa with a 2 I % yield and 4.2-fold. Response surface regression was used to predict the maximum fructose levels achievable under the combinations of temperature, enzyme dosage and incubation time. A reaction time (48 h), enzyme dosage (100 U/ml) and inulin concentration (150 g/l) at pH 5.0 at 50°C gave higher fructose levels (106.6 mg/ml) using crude exoinulinase as compared to 98.43 mg/ml using the purified exoinulinase. These findings indicate that higher levels of fructose require longer incubation periods and higher inulin substrate concentrations with higher enzyme dosage. The crude exoinulinase preparation gave fairly higher levels of fructose than the purified exoinulinase and this is due to the presence of other hydrolytic enzymes in the crude preparation. The conditions established by RSM and CCO were adequate in producing high yield of oligosaccharides and fructose and can therefore be applied for their industrial production since they are in high demand due to their health benefits as prebiotics.
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Queens, pseudoqueens and laying workers reproductive competition in the Cape Honeybee (Apis mellifera capensis Eschscholtz)
- Authors: Muerrle, Thomas Martin
- Date: 2008
- Subjects: Honeybee Honeybee -- Reproduction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5750 , http://hdl.handle.net/10962/d1005437
- Description: In honeybees (Apis mellifera L.) the queen monopolises reproduction. However, especially after queen loss, workers can lay eggs, but are unable to mate. They produce haploid male offspring (drones) from unfertilised eggs via arrhenotokous parthenogenesis. In contrast, workers of the honeybee subspecies Apis mellifera capensis Eschscholtz typically produce diploid female offspring from unfertilised eggs thelytokously. After queen loss and without queen-derived brood A. m. capensis colonies can successfully requeen from worker-derived brood. This, however, is a relatively rare event in wild populations. Moreover, workerderived queens were described to be smaller, more worker-like and reproductively inferior. On the other hand, the fixation of the thelytokous trait relies mainly on sufficient numbers of viable drones produced by worker-derived queens. Small numbers of reproductively inferior worker-derived queens in A. m. capensis populations would be clearly counterintuitive. It is therefore necessary to quantify the significance of worker-dependant queen rearing pathways on the individual (queen) and on population level.Reproductive inferiority of worker-derived queens could not be confirmed on the individual (queen) level when comparing parameters indicating potential reproductive success of queen- and worker-derived queens. Queen- and worker-derived queens clearly showed a congruent range of reproductive performance. In queen rearing preference tests, increased acceptance of worker-derived female larvae was exactly counterbalanced by increased mortality, resulting in an equal number of eclosing virgin queens from an equal number of grafts in both test groups. Larval survival and successful eclosion is a prerequisite for a queen’s reproductive success. I found no difference in eclosion success for queen- and worker-derived virgin queens, indicating a similar potential for reproductive success in both queen types. Assessments of the developmental patterns of colonies headed by both queen and worker-derived queens in long-term experiments revealed no significant differences in reproductive success. Colonies headed by queen-derived queens and colonies headed by worker-derived queens could not be separated when comparing the different developmental pathways observed or from differences in worker-force. Reproductive dominance in A. m. capensis appeared tobe determined by a function of relative compositional and absolute quantitative pheromonal patterns, where individuals, which produce compositionally most queen-like blends in highest quantities, occupy top positions. Queen- and worker-derived virgin queens occupied intermediate positions between pseudoqueens and mated queens. However, no significant differences between the pheromonal status of queen- and worker-derived virgin queens were observed, suggesting a similar range of reproductive dominance for both queen types. In behavioural bioassays queen- and worker-derived virgin queens appeared to be similarly attractive to clustering workers and to drones in a drone congregation area, indicating no differences in potential reproductive success for queens from both origins for those parameters. The significant influence of the queen substance 9-ODA on attractiveness to workers and drones was confirmed. Rare requeening events from worker-derived female brood in queenless A.m. capensis do not satisfactorily explain the fixation of the thelytokous trait at a population level. I observed A. m. capensis worker ovipositing into empty artificial queen cell cups in queen-right colonies. The queen was confined behind a queen excluder grid in a separate compartment of the colony, to imitate reduced pheromonal flow, similar to swarming or superseding colonies. Eggs oviposited by workers in artificial queen cell cups were readily accepted for queen rearing and successful eclosion of viable virgin queens was observed. Consequently I suggested an alternative worker-dependant reproductive pathway in A. m. capensis, which was never described before: In swarming or superseding queenright colonies, laying workers may directly compete with the queen for reproductive success by ovipositing (instead of the queen) into natural queen cell cups. At a population level this reproductive tactic may result in large numbers of worker-derived queens of high reproductive quality in natural populations of A. m. capensis.
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Radio Frequency Identification (RFID) adoption in the South African retail sector: an investigation of perceptions held by members of the retail sector regarding the adoption constraints
- Authors: Liu, Haidi
- Date: 2008
- Subjects: Radio frequency identification systems , Retail trade -- South Africa , Business logistics -- Management -- South Africa , Retail trade -- Employees -- South Africa , Retail trade -- Technological innovations , Radio waves , Consumer profiling
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:1144 , http://hdl.handle.net/10962/d1002774 , Radio frequency identification systems , Retail trade -- South Africa , Business logistics -- Management -- South Africa , Retail trade -- Employees -- South Africa , Retail trade -- Technological innovations , Radio waves , Consumer profiling
- Description: Radio Frequency Identification (RFID) technology is a ethod of identifying unique items using radio waves that communicate between RFID tags and readers without line-of-sight readability. RFID technology provides great potential in many industries and a wide spectrum of possible uses. Areas of application include person identification, logistics, pharmaceutical, access control, security guard monitoring and asset management. One of the areas where RFID is being used and where it promises excellent results is the retail industry. While RFID systems have the potential to revolutionise the way products and goods are tracked and traced in the retail supply chain, barriers to its widespread adoption exist: for example; technical constraints, return on investment constraints, a lack of awareness and education and as well as privacy and security issues. The research aims to identify the barriers to the adoption of RFID and to investigate the perceptions of RFID held by members of the retail sector in South Africa (SA). Current research and available literature are used to identify RFID adoption barriers and a conceptual framework on this subject is proposed, which is then verified by SA retailers’ perceptions, established by means of a survey. Initial barriers to widespread adoption include a shortage in skills, a lack of standards, high costs associated with RFID devices, the difficulty of integrating with current legacy systems, and a lack of familiarity with the system. Finally, an enhanced framework is proposed, describing RFID adoption barriers within the South African retail sector. In summary, the framework is an outline of the barriers impacting RFID adoption in the SA retail sector that need to be considered and addressed. The framework identifies six categories of RFID adoption barriers, with each category containing two or more barriers relating to that particular category. These categories are Technological, Cost and return on investment, Privacy and security, Implementation, Organisational factors and People.
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Ray Charles: a psychobiographical study
- Authors: Biggs, Ilze
- Date: 2008
- Subjects: Charles, Ray, 1930-2004 Psychology -- Biographical methods -- Case studies Jazz singers -- Biography Blind entertainers -- Psychology
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2933 , http://hdl.handle.net/10962/d1002442
- Description: Psychobiography is the formulation of an individual's narrative according to a psychological theory. Psychobiographical researchers face a number of challenges. One pertinent challenge is the limited amount of psychobiographical research conducted at academic institutions, including South Africa. Although a number of studies had been completed in the past decade, the impact of psychobiographical research remains negligible. Although much has been written about Ray Charles, none of the existing literature adopted a specific psychological focus. Charles developed from a young boy in a poverty stricken, racially segregated society into an exceptionally successful musician who worked productively until he died at the age of 73. He was selected as the subject on the basis of interest value, uniqueness and significance of life achievements. The primary aim of this study was to explore and describe the development of Charles according to Levinson's (Levinson, et. ai, 1978) theoretical framework. Levinson's theory of adult development identifies and describes the important changes that occur throughout the lifespan of an individual. A secondary aim was to provide an understanding of Charles within the social, economic and historical context in which he lived. The data collection and analysis was conducted according to Yin's (2003) 'analytic generalization'. The data was analysed according to three linked sub-processes proposed by Huberman and Miles (1994).
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Re-evaluating the law of vicarious liability in South Africa
- Authors: Small, Jonathan Noel
- Date: 2008
- Subjects: Independent contractors -- South Africa Law -- South Africa Torts -- South Africa Courts -- South Africa Jurisdiction -- South Africa International law -- South Africa Roman law Roman-Dutch law
- Language: English
- Type: Thesis , Masters , LLM
- Identifier: vital:3704 , http://hdl.handle.net/10962/d1004771
- Description: This thesis is an analysis of the law of vicarious liability and its application within the legal framework of delict in South Africa. A brief overview of the historical development of this branch of law is given, with reference to the influences of Roman, Roman-Dutch and English law. That is followed by an exposition of the 'modem' interpretation of vicarious liability as applied in South African courts, highlighting apparent inconsistencies and the need for reform in what has become a persistently controversial area of law. Specific attention is paid to the so-called 'course and scope enquiry' and to the enduring difficulties associated with attributing liability to employers for the deliberate wrongful conduct of their employees. It is argued that the courts have yet to reach consensus on a general principle capable of being applied to the facts of so-called 'deviation cases', and that consequently the legal divergence on these matters gives rise to uncertainty and concern. It is submitted that the way in which the traditional test for vicarious liability is currently applied fails to give true effect to the policy considerations upon which this branch of law is founded. By way of comparison with the South African position, a detailed account of the law of vicarious liability in comparable foreign jurisdictions is given, with emphasis placed on recent developments in England and the British Commonwealth. The study then moves to an analysis of the various policy considerations behind vicarious liability, with particular attention being paid to the role of risk-related liability and the role of risk-assumption in the 'course and scope' enquiry. A comparative analysis follows, highlighting differences between the approaches of the foreign jurisdictions and that taken by the South African courts. The work concludes with a proposal that the South African courts should broaden the scope of vicarious liability and opt for a model similar to that which has recently been adopted in Canada.
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Reading nonsense : a journey through the writing of Edward Lear
- Authors: Pendlebury, Kathleen Sarah
- Date: 2008
- Subjects: Lear, Edward, 1812-1888 Lear, Edward, 1812-1888 Criticism and interpretation English poetry -- 19th century -- Criticism and interpretation
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2206 , http://hdl.handle.net/10962/d1002249
- Description: In this thesis I have addressed some of the problems that have arisen in critical approaches to the nonsense works of Edward Lear from the late nineteenth century. I have entitled it “Reading Nonsense” because my central concern is with how best to apprehend the paradoxes inherent in literary nonsense, which inevitably raises interpretative questions. Because nonsense is a “basic type of communication” whose essence is “unresolved tension between [the] presence and absence of meaning” (Tigges, Anatomy 51), we are called upon either to “make sense of” that which claims to offer up no meaning or to surrender ourselves to meaninglessness. Broadly, critical approaches to nonsense fall into two classes: those that maintain that nonsense is not, in fact, “not sense”, but rather a kind of symbolic language that can be reconciled into meaning; and those which uphold the nonsensicality of nonsense, maintaining that certain ambiguities and paradoxes cannot be accounted for, and it is inappropriate to try to do so. In addition, Lear’s texts are situated in various traditions of writing for children and adults and in the distinctive setting of the Victorian era; and these cultural and literary influences play an important role in the interpretation and misinterpretation of nonsense. My first chapter comprises a mise en scène of the genre of literary nonsense; while in Chapter 2 I turn to the cultural backdrop of Lear’s nonsense in particular, and examine one of the claims frequently made in nonsense criticism: that Lear’s literary nonsense is distinctively “Victorian”. Chapter 3, “How to Read a Learian Limerick”, rests on the exegesis of nonsense that appears in Chapter 1, for here I propose a technique for reading Lear’s limericks that preserves both their “sensical” and nonsensical elements in contrast to critical analyses that attempt to reconcile the nonsense into a code. In Chapter 4 I examine Lear’s songs from the critical perspectives of nonsense and of romanticism. Finally, in conclusion, I consider the role and significance of humour in nonsense, and gesture towards further possible explorations, including in the appendix my essay on the nonsense poetry of South African writer Philip de Vos.
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Reconstructing ionospheric TEC over South Africa using signals from a regional GPS network
- Authors: Opperman, B D L
- Date: 2008
- Subjects: Global Positioning System Global Positioning System -- Data processing Electrons -- South Africa Ionosphere -- South Africa Ionospheric radio wave propagation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5487 , http://hdl.handle.net/10962/d1005273
- Description: Radio signals transmitted by GPS satellites orbiting the Earth are modulated as they propagate through the electrically charged plasmasphere and ionosphere in the near-Earth space environment. Through a linear combination of GPS range and phase measurements observed on two carrier frequencies by terrestrial-based GPS receivers, the ionospheric total electron content (TEC) along oblique GPS signal paths may be quantified. Simultaneous observations of signals transmitted by multiple GPS satellites and observed from a network of South African dual frequency GPS receivers, constitute a spatially dense ionospheric measurement source over the region. A new methodology, based on an adjusted spherical harmonic (ASHA) expansion, was developed to estimate diurnal vertical TEC over the region using GPS observations over the region. The performance of the ASHA methodology to estimate diurnal TEC and satellite and receiver differential clock biases (DCBs) for a single GPS receiver was first tested with simulation data and subsequently applied to observed GPS data. The resulting diurnal TEC profiles estimated from GPS observations compared favourably to measurements from three South African ionosondes and two other GPS-based methodologies for 2006 solstice and equinox dates. The ASHA methodology was applied to calculating diurnal two-dimensional TEC maps from multiple receivers in the South African GPS network. The space physics application of the newly developed methodology was demonstrated by investigating the ionosphere’s behaviour during a severe geomagnetic storm and investigating the long-term ionospheric stability in support of the proposed Square Kilometre Array (SKA) radio astronomy project. The feasibility of employing the newly developed technique in an operational near real-time system for estimating and dissimenating TEC values over Southern Africa using observations from a regional GPS receiver network, was investigated.
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Reflective accounts of childhood inter-species experiences in a Southern-African context: a phenomenological-hermeneutic exploration
- Authors: Rump, Samantha
- Date: 2008
- Subjects: Child psychology -- South Africa Child development -- South Africa Human-animal relationships -- South Africa Children and animals -- South Africa Animal psychology -- South Africa Hermeneutics Phenomenology
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:3045 , http://hdl.handle.net/10962/d1002554
- Description: The aims of this research were to describe in rich phenomenological detail the recollected childhood experiences described by three South African adults of growing up with animals in the context of a traditionally African cultural perspective in South Africa; as well as to document the emotional, physical and social effects of inter-species relationships as described by these participants, in order to explore and situate these experiences in relation to broad international perspectives on the contribution of animals to human development. The question of how these described experiences correlate with broad international perspectives on the contribution of animals to human development comprised the hermeneutic of the study. Here it was found that the experiences of these South African individuals were generally in keeping with the trends found in the literature. Participants attributed to their childhood relationships with animals a variety of benefits. These benefits occur on a range of levels, from the physical to the cognitive, and the psychosocial. The emotional attachment of the participants to animals with whom they had interacted in childhood correlated with the nature of interspecies relationships as anticipated by the literature. Cultural differences in the conceptualisation of inter-species relationships, between western and traditionally African ideologies, appeared to influence the moral and ethical positions assumed by the participants, while the subjective nature of the described attachment between participants and animals remains qualitatively similar across cultures, when explored in relation to international research. The similarities between the experiences of the participants and international research findings lend credence to Wilson’s hypothesis that all human beings are potentially able to connect in deep and profound ways with their natural environment, and that this connection contributes to the development of social and cognitive skills, as well as constituting emotional support and stability. The research concludes with an examination of its own limitations and suggestions are made for further research.
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Removal and photocatalysis of 4-Nitrophenol using metallophthalocyanines
- Authors: Marais, Eloise Ann
- Date: 2008
- Subjects: Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4343 , http://hdl.handle.net/10962/d1005005 , Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Description: Photodegradation of 4-nitrophenol (4-Np) in the presence of water-soluble zinc phthalocyanines and water-insoluble metallophthalocyanines is reported. The water-soluble phthalocyanines employed include zinc tetrasulphophthalocyanine (ZnPcS[subscript 4]), zinc octacarboxyphthalocyanine (ZnPc(COOH)[subscript 8]) and a sulphonated ZnPc containing a mixture of differently sulphonated derivatives (ZnPcS[subscript mix]), while the water-insoluble phthalocyanines used include unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring-substituted zinc tetranitro (ZnPc(NO[subscript 2])[subscript 4]), zinc tetraamino (ZnPc(NH[subscript 2])[subscript 4]), zinc hexadecafluoro (ZnPcF[subscript 16]) and zinc hexadecachloro (ZnPcCl[subscript 16]) phthalocyanines. The most effective water-soluble photocatalyst is ZnPcS[subscript mix] in terms of the high quantum yield obtained for 4-Np degradation (Φ[subscript 4-Np]) as well as its photostability. While ZnPc(COOH)[subscript 8] has the highest Φ[subscript 4-Np] value relative to the other water-soluble complexes, it degrades readily during photocatalysis. The Φ[subscript 4-Np] values were closely related to the singlet oxygen quantum yields Φ[subscript Δ] and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPcS[subscript mix] and 7.7 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPc(COOH)[subscript 8]. ClAlPc is the most effective photocatalyst relative to the other heterogeneous photocatalysts for the phototransformation of 4-Np, with 89 ± 8.4 % degradation of 4-Np achieved after 100 min. The least effective catalysts were ZnPcCl[subscript 16] and MgPc. The final products of the photocatalysis of 4-Np in the presence of the homogeneous photocatalysts include 4-nitrocatechol and hydroquinone, while degradation of 4-Np in the presence of the heterogeneous photocatalysts resulted in fumaric acid and 4-nitrocatechol. ClAlPc was employed for the heterogeneous photocatalysis of the non-systemic insecticide, methyl paraoxon. Complete degradation of the pesticide was confirmed by the disappearance of the HPLC trace for methyl paraoxon after 100 min of irradiation with visible light. The removal of 4-Np from an aqueous medium using commercially available Amberlite[superscript ®] IRA-900 modified with metal phthalocyanines was also investigated. The metallophthalocyanines immobilised onto the surface of Amberlite[superscript ®] IRA-900 include Fe (FePcS[subscript 4]), Co (CoPcS[subscript 4]) and Ni (NiPcS[subscript 4]) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcS[subscript mix]), Co (CoPcS[subscript mix]) and Ni (NiPcS[subscript mix]). Adsorption rates were fastest for the modified adsorbents at pH 9. Using the Langmuir-Hinshelwood kinetic model, the complexes showed the following order of 4-Np adsorption: CoPcS[subscript mix] > NiPcS[subscript 4] > NiPcS[subscript mix] > FePcS[subscript 4] > FePcS[subscript mix] > CoPcS[subscript 4]. The adsorbents were regenerated using dilute HNO[subscript 3], with 76 % (7.6 x 10[superscript -5] mol) of 4-Np recovered within 150 min.
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Revised parameter estimation methods for the Pitman monthly rainfall-runoff model
- Authors: Kapangaziwiri, Evison
- Date: 2008
- Subjects: Rain and rainfall -- Mathematical models , Runoff -- Mathematical models , Hydrology -- Mathematical models , Water supply -- South Africa , Water resources development -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:6033 , http://hdl.handle.net/10962/d1006172 , Rain and rainfall -- Mathematical models , Runoff -- Mathematical models , Hydrology -- Mathematical models , Water supply -- South Africa , Water resources development -- South Africa
- Description: In recent years, increased demands have been placed on hydrologists to find the most effective methods of making predictions of hydrologic variables in ungauged basins. A huge part of the southern African region is ungauged and, in gauged basins, the extent to which observed flows represent natural flows is unknown, given unquantified upstream activities. The need to exploit water resources for social and economic development, considered in the light of water scarcity forecasts for the region, makes the reliable quantification of water resources a priority. Contemporary approaches to the problem of hydrological prediction in ungauged basins in the region have relied heavily on calibration against a limited gauged streamflow database and somewhat subjective parameter regionalizations using areas of assumed hydrological similarity. The reliance of these approaches on limited historical records, often of dubious quality, introduces uncertainty in water resources decisions. Thus, it is necessary to develop methods of estimating model parameters that are less reliant on calibration. This thesis addresses the question of whether physical basin properties and the role they play in runoff generation processes can be used directly in the estimation of parameter values of the Pitman monthly rainfall-runoff model. A physically-based approach to estimating the soil moisture accounting and runoff parameters of a conceptual, monthly time-step rainfall-runoff model is proposed. The study investigates the physical meaning of the model parameters, establishes linkages between parameter values and basin physical properties and develops relationships and equations for estimating the parameters taking into account the spatial and temporal scales used in typical model applications. The estimationmethods are then tested in selected gauged basins in southern Africa and the results of model simulations evaluated against historical observed flows. The results of 71 basins chosen from the southern African region suggest that it is possible to directly estimate hydrologically relevant parameters for the Pitman model from physical basin attributes. For South Africa, the statistical and visual fit of the simulations using the revised parameters were at least as good as the current regional sets, albeit the parameter sets being different. In the other countries where no regionalized parameter sets currently exist, simulations were equally good. The availability, within the southern African region, of the appropriate physical basin data and the disparities in the spatial scales and the levels of detail of the data currently available were identified as potential sources of uncertainty. GIS and remote sensing technologies and a widespread use of this revised approach are expected to facilitate access to these data.
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Rhodes University during the segregation and apartheid eras, 1933 to 1990
- Authors: Greyling, Sean Andrew
- Date: 2008
- Subjects: Rhodes University -- History Post-apartheid era -- South Africa -- History College students -- South Africa -- Political activity South Africa -- Race relations -- History -- 20th century South Africa -- Politics and government -- 20th century
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2545 , http://hdl.handle.net/10962/d1002397
- Description: In 2004 Rhodes University celebrated its centenary. At a Critical Tradition Colloquium opportunity was given to explore the university’s past. In particular, its liberal image was questioned and its role during apartheid brought under scrutiny. This thesis investigates the questions raised at the Colloquium. It aims to cover the whole apartheid era in one coherent narrative by addressing the history of Rhodes during that era and how it handled issues of race and politics. It begins in 1933, when the first black student applied to Rhodes, and ends in 1990, when apartheid was drawing to a close.
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Risk assessment and the effects of overhead work - an automotive industry example
- Authors: Elliott, Andrew Brent
- Date: 2008
- Subjects: Human engineering -- South Africa , Industrial safety -- South Africa , Automobile industry workers -- South Africa -- Health risk assessment , Automobile industry and trade -- South Africa -- Safety measures , Musculoskeletal system -- Wounds and injuries -- Prevention , Lifting and carrying -- Safety measures , Work measurement , Posture
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5132 , http://hdl.handle.net/10962/d1005211 , Human engineering -- South Africa , Industrial safety -- South Africa , Automobile industry workers -- South Africa -- Health risk assessment , Automobile industry and trade -- South Africa -- Safety measures , Musculoskeletal system -- Wounds and injuries -- Prevention , Lifting and carrying -- Safety measures , Work measurement , Posture
- Description: The focus of this investigation was an analysis of the work demands being placed on South African automotive industry workers as there is a recognised problem with regard to the prevalence of musculoskeletal disorders (MSDs). Preliminary work was conducted to highlight the dominant risks and areas which elicited higher numbers of MSDs within the chosen automotive plant. An area of concern was highlighted through medical record analysis and the use of risk assessment tools, thereby prioritising the need for ergonomic intervention. In particular, the effects of varying restricted and overhead work heights on the biomechanical, physiological and psychophysical responses of an individual were investigated. Twenty-eight subjects were required to complete sixteen conditions. The conditions consisted of the adoption of restricted and upright overhead static postures, with half requiring the holding of four kilograms of weight in the hands and the remaining eight conditions having no weight. Testing was carried out using an electromyography unit, ergospirometer and a perceptual Body Discomfort Map and Scale. This involved a habituation and testing session. The results of the testing revealed the biomechanical and physiological responses were dependant on the change in height. Body discomfort was also shown to be variable over the changing height conditions. This indicates that there is a significant effect of height on an individual’s responses during overhead work. The extreme restricted (-200mm and -100mm) and upright (+300mm and +400mm) overhead conditions within this study were limiting, as they elicited the highest muscle activation, physiological responses and body discomfort ratings. Positions that are preferable to adopt, which were identified from the results in this study, indicate conditions closer to head height (0mm and +100mm) were favourable. The results therefore illustrate how awkward working postures during work are likely to elicit higher demands from an individual, which could lead to an increased risk for the development of a musculoskeletal disorder. The added factor of weight elicited significant results over all variables, excluding a respiratory The focus of this investigation was an analysis of the work demands being placed on South African automotive industry workers as there is a recognised problem with regard to the prevalence of musculoskeletal disorders (MSDs). Preliminary work was conducted to highlight the dominant risks and areas which elicited higher numbers of MSDs within the chosen automotive plant. An area of concern was highlighted through medical record analysis and the use of risk assessment tools, thereby prioritising the need for ergonomic intervention. In particular, the effects of varying restricted and overhead work heights on the biomechanical, physiological and psychophysical responses of an individual were investigated. Twenty-eight subjects were required to complete sixteen conditions. The conditions consisted of the adoption of restricted and upright overhead static postures, with half requiring the holding of four kilograms of weight in the hands and the remaining eight conditions having no weight. Testing was carried out using an electromyography unit, ergospirometer and a perceptual Body Discomfort Map and Scale. This involved a habituation and testing session. The results of the testing revealed the biomechanical and physiological responses were dependant on the change in height. Body discomfort was also shown to be variable over the changing height conditions. This indicates that there is a significant effect of height on an individual’s responses during overhead work. The extreme restricted (-200mm and -100mm) and upright (+300mm and +400mm) overhead conditions within this study were limiting, as they elicited the highest muscle activation, physiological responses and body discomfort ratings. Positions that are preferable to adopt, which were identified from the results in this study, indicate conditions closer to head height (0mm and +100mm) were favourable. The results therefore illustrate how awkward working postures during work are likely to elicit higher demands from an individual, which could lead to an increased risk for the development of a musculoskeletal disorder. The added factor of weight elicited significant results over all variables, excluding a respiratory individual.
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Solar cycle effects on GNSS-derived ionospheric total electron content observed over Southern Africa
- Authors: Moeketsi, Daniel Mojalefa
- Date: 2008
- Subjects: Ionosphere -- Africa, Southern Electrons Ionospheric electron density -- Africa, Southern Ionosondes -- Africa, Southern Electromagnetic waves
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5489 , http://hdl.handle.net/10962/d1005275
- Description: The South African Global Navigation Satellite System (GNSS) network of dual frequency receivers provide an opportunity to investigate solar cycle effects on ionospheric Total Electron Content (TEC) over the South Africa region by taking advantage of the dispersive nature of the ionospheric medium. For this task, the global University of New Brunswick Ionospheric Modelling Technique (UNB-IMT) was adopted, modified and applied to compute TEC using data from the southern African GNSS Network. TEC values were compared with CODE International GNSS services TEC predictions and Ionosonde-derived TEC (ITEC) measurements to test and validate the UNB-IMT results over South Africa. It was found that the variation trends of GTEC and ITEC over all stations are in good agreement and show pronounced seasonal variations with high TEC values around equinoxes for a year near solar maximum and less pronounced around solar minimum. Signature TEC depletions and enhanced spikes were prevalently evident around equinoxes, particularly for a year near solar maximum. These observations were investigated and further discussed with an analysis of the midday Disturbance Storm Time (DST) index of geomagnetic activity. The residual GTEC – ITEC corresponding to plasmaspheric electron content and equivalent ionospheric foF2 and total slab thickness parameters were computed and comprehensively discussed. The results verified the use of UNB-IMT as one of the tools for ionospheric research over South Africa. The UNB-IMT algorithm was applied to investigate TEC variability during different epochs of solar cycle 23. The results were investigated and further discussed by analyzing the GOES 8 and 10 satellites X-ray flux (0.1 – 0.8 nm) and SOHO Solar Extreme Ultraviolet Monitor higher resolution data. Comparison of UNB-IMT TEC derived from collocated HRAO and HARB GNSS receivers was undertaken for the solar X17 and X9 flare events, which occurred on day 301, 2003 and day 339, 2006. It was found that there exist considerable TEC differences between the two collocated receivers with some evidence of solar cycle dependence. Furthermore, the daytime UNB TEC compared with the International Reference Ionosphere 2001 predicted TEC found both models to show a good agreement. The UNB-IMT TEC was further applied to investigate the capabilities of geodetic Very Long Baseline Interferometry (VLBI) derived TEC using the Vienna TEC Model for space weather monitoring over HartRAO during the CONT02 and CONT05 campaigns conducted during the years 2002 (near solar maximum) and 005 (near solar minimum). The results verified the use of geodetic VLBI as one of the possible instruments for monitoring space weather impacts on the ionosphere over South Africa.
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South Africa and Malaysia: identity and history in South-South relations
- Authors: Haron, Muhammed
- Date: 2008
- Subjects: Critical theory South Africa -- Foreign relations -- Malaysia Malaysia -- Foreign relations -- South Africa South Africa -- Politics and government -- History Malaysia -- Politics and government -- History South Africa -- Politics and government Malaysia -- Politics and government South Africa -- Social conditions -- History Malaysia -- Social conditions -- History South Africa -- Economic conditions Malaysia -- Economic conditions
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2780 , http://hdl.handle.net/10962/d1002990
- Description: The focus of this thesis is on the bilateral relationship between South Africa and Malaysia. The thesis appropriates ‘critical theory,’ and as a flexible theoretical tool, and, as an open-ended, loose frame in order to give voice to the marginalized and voiceless from the South. The thesis thus looks at the politico-economic ties that have been developed and brings into view the socio-cultural relations that had been established between the peoples of the two sovereign nation-states during the apartheid and post-apartheid eras respectively. The basic purpose of this study was fivefold: (a) to contribute to the extant literature that concentrates on South Africa’s relations with Malaysia, (b) to examine the relationship at political and economic ties in some detail, (c) to demonstrate that apart from the afore-mentioned bonds IR specialists should also take into account the socio-cultural dimensions of international relations, (d) to bring to light the nation-state’s limitations when discussing the role of non-state actors and considering the contributions of other factors such as globalization, and (e) to stimulate further research on bilateral and multilateral relations in the South – particularly between South Africa and other states in Asia and Latin America - that would assist to better understand the past, present and perhaps the future.
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Spatial and temporal variations in metals in the sediment and water of selected Eastern Cape Estuaries, South Africa
- Authors: Orr, Kyla Kathleen
- Date: 2008
- Subjects: Marine sediments -- South Africa -- Eastern Cape , Metals -- South Africa -- Eastern Cape , Metals -- Environmental aspects , Estuaries -- South Africa -- Eastern Cape , Estuarine ecology -- South Africa -- Eastern Cape , Estuarine sediments -- South Africa -- Eastern Cape , Water quality -- South Africa -- Eastern Cape , Water pollution -- South Africa -- Eastern Cape , Environmental toxicology -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5769 , http://hdl.handle.net/10962/d1005457 , Marine sediments -- South Africa -- Eastern Cape , Metals -- South Africa -- Eastern Cape , Metals -- Environmental aspects , Estuaries -- South Africa -- Eastern Cape , Estuarine ecology -- South Africa -- Eastern Cape , Estuarine sediments -- South Africa -- Eastern Cape , Water quality -- South Africa -- Eastern Cape , Water pollution -- South Africa -- Eastern Cape , Environmental toxicology -- South Africa -- Eastern Cape
- Description: The spatio-temporal patterns in concentrations of selected metals within the sediment (Cd, Co, Cu, Fe, Pb, Ni and Zn) and water (Cd and Pb) of three permanently open estuaries (Kariega, Kowie, Great Fish) and six temporary open-closed estuaries (Mpekweni, East Kleinemonde, West Kleinemonde, Riet, Kasouga, Boknes) were investigated. The concentrations of metals were influenced by size composition and total organic content of the sediments. Enrichment factors (EFs), using Fe as a reference element, and baseline linear regression models for metals vs. Fe were calculated to assess the extent of metal enrichment in the sediments. The mean concentrations of metals in the sediments(mg·kg⁻¹) showed ranges of 0.28 – 2.31 for Cd, 1.26 – 6.24 Co, 0.69 – 6.93 for Cu, 2119 – 14912 for Fe, 2.29 –14.01 for Ni, 4.81 – 22.20 for Pb and 5.77 – 21.75 for Zn. Mean normalized enrichment factors ranged between 0.75 – 6.19 for Cd, 0.53 – 2.71 for Co, 0.22 – 0.84 for Cu, 0.30 – 1.87 for Ni, 0.99 – 3.17 for Pb and 0.14 – 0.98 for Zn. All nine estuaries had average enrichment factors of greater than 1 for Cd. In general there was no enrichment of Cu and Zn in the sediments of any of the estuaries included in this study (EFs < 1). The Kariega, East Kleinemonde, West Kleinemonde, Riet and Great Fish Estuaries showed some degree of enrichment for Co (1 < EF < 4), Ni (1 < EF < 2) and Pb (1 < EF < 4), while the Mpekweni, Kasouga, Boknes and Kowie Estuaries were unenriched with these metals (EF < 1). Enrichment factors for Cd, Co and Pb typically followed the development gradient along the estuaries, suggesting anthropogenic enrichment. The concentrations of Cd and Pb in the water of the nine estuaries were also determined. The average concentrations of Cd and Pb in the water (μg·ℓ⁻¹) ranged between 0.05 – 3.32 and 0.75 – 34.13 respectively. On average the concentrations of Cd and Pb in the water of all the estuaries were below the South African recommended water quality guidelines for coastal marine waters. Variations in metal concentrations associated with changes in hydrology (wet vs. dry season) were determined in the water and sediment of the Kariega, East Kleinemonde and Riet Estuaries. Cobalt, Pb and Ni enrichment in the Kariega Estuary sediment was significantly higher during the dry season, and the mean concentrations of Pb and Cd in the water column were 19-fold and 66-fold higher in the dry season. The elevated concentration of metals during the dry season could be related to accumulation of diffuse pollution from human activities within the catchment area. Conversely, inflow of fresh water into the estuary had the net effect of reducing the concentration and enrichment of these metals within the Kariega Estuary due to scouring and outflow of estuarine water and sediment into the marine environment. The temporal variations in metal concentrations and enrichment factors were less pronounced in the temporary open-closed estuaries than the permanently open Kariega Estuary. The observed trend can probably be related to the low anthropogenic impact within the catchment areas of these systems, and the relatively smaller size of the catchments. Significant spatial variations existed in metal enrichment in the sediment of both the East Kleinemonde and Riet estuaries, with the highest degrees of enrichment occurring in the sediments from the marine environment and lower reaches.
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Stakeholders' perceptions of the shift to democratic leadership in a secondary school in the Eastern Cape : a case study
- Authors: Lombo, Mzimkhulu Solomon
- Date: 2008
- Subjects: Education -- South Africa -- Eastern Cape , Education and state -- South Africa -- Eastern Cape , Education -- Political aspects -- South Africa -- Eastern Cape , Education, Secondary -- South Africa -- Eastern Cape -- Case studies , Educational change -- South Africa -- Eastern Cape , Educational leadership -- South Africa -- Eastern Cape , School management and organization -- South Africa -- Eastern Cape , South Africa -- Politics and government -- 1994-
- Language: English
- Type: Thesis , Masters , MEd
- Identifier: vital:2001 , http://hdl.handle.net/10962/d1015541
- Description: The advent of political democracy in South Africa in 1994 gave rise to new policy in education promoting democratic and participative ways of managing and leading schools. The intention was both to break from the apartheid past which was characterised by an authoritarian, nonparticipative mindset, as well as to point the way for future education development. Principals of schools were expected to develop structures and adopt management and leadership styles which were participative, inclusive and developmental. Many principals would not have been prepared for this shift in mindset, and notions of full participation in governance by parents, and representation of learners through constituted bodies would have been new to them. In this case study of one semi-urban secondary school in the Eastern Cape the researcher sought to establish whether and to what extent the school had moved towards the new management and leadership approaches. The study is interpretive in orientation, and made use of interviews and document analysis. This research has found that the school had democratised its management and leadership to a considerable degree, but that this was not necessarily due to profound changes on the part of the principal 's leadership. The principal emerged as a democratic leader by nature. More significant seem to be the structures which the school had put in place, both officially and internally, to promote widespread participation and the distribution of leadership. This decentralised system of management has contributed to a distinct organisation culture in the school characterised by warmth, openness and ubuntu.
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State sovereignty and alternative community in southern Africa: exploring the Zion Christian Church as the building block for deeper notions of regional community
- Authors: Radebe, Zandisiwe
- Date: 2008
- Subjects: Zionist Christian Church Southern African Development Community Community development -- Africa, Southern Regionalism -- Africa, Southern Sovereignty -- Africa, Southern Africa, Southern -- Economic integration
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2824 , http://hdl.handle.net/10962/d1003034
- Description: Regional community in southern Africa has been limited to the region’s states. As a result, deeper notions of community emanating from non-state actors, particularly transnational social movements, continue to be ignored. In an attempt to transcend state centrism, this thesis highlights alternative forms of regional community by exploring the Zion Christian Church (ZCC), one of southern Africa’s biggest and fastest growing cross-border movements. The ZCC is a potential agent for developing regional community from the bottom-up, driving a people-oriented regional integration approach in southern Africa. The ZCC, with its extensive following among the region’s poor, offers a compelling example of a grassroots and truly bottom-up approach to regional community. This thesis explores the possibility of the ZCC as a model of alternative community and identity centred on people’s daily experiences and grounded in a shared history and solidarity. It seeks to highlight the significance of transnational movements like the ZCC to policy makers in the region and it argues that grassroots communities are marching ahead of SADC member states and politicians in the area of integration. There exists a transnational cooperation amongst followers of the ZCC and other grassroots communities across the region and this cooperation transcends the traditional notion of state sovereignty, thereby highlighting deeper notions of what it means to be a community at regional level.
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Studies directed towards the synthesis of chromone carbaldehyde-derived HIV-1 protease inhibitors
- Authors: Molefe, Duduzile Mabel
- Date: 2008
- Subjects: Protease Inhibitors , HIV infections , HIV (Viruses) , AIDS (Disease) , Proteolytic enzymes , Heterocyclic compounds -- Derivatives , Chemical kinetics , Nuclear magnetic resonance spectroscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4526 , http://hdl.handle.net/10962/d1015542
- Description: A series of chromone-3-carbaldehydes have been prepared using Vilsmeier-Haack methodology while a corresponding series of chromone-2-carbaldeydes have been synthesized via the Kostanecki-Robinson reaction. Baylis-Hillman reactions have been conducted on both series of chromone carbaldehydes using three different catalysts, viz., 1,4-diazabicyclo(2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) and 3-hydroxyquinuclidine (3HQ), and acrylonitrile, methyl acrylate and methyl vinyl ketone as the activated alkenes. These reactions have typically (but not always!) afforded both normal Baylis-Hillman and dimeric products. Attention has also been given to the use of 1-methyl-2-pyrrolidine (1-NMP), an ionic liquid, to replace normal organic solvents, and it has been found that, in the presence of DABCO, chromone-3-carbaldehydes afford the dimeric products alone. Reactions of chromone-3-carbaldehydes with methyl vinyl ketone have yielded unexpected, novel adducts, which appear to arise from preferential attack at C(2) in the chromone nucleus. Research on chromone-2-carbaldeydes under Baylis-Hillman conditions has also resulted in the formation of some interesting products instead of the expected Baylis-Hillman adducts. The Baylis-Hillman products have been explored as substrates for aza-Michael reactions using various amino derivatives including protected amino acids in the presence of the tetrabutylammonium bromide (TBAB) and the ionic liquid, 3-butyl-1- methylimidazoleboranetetrafluoride (BmimBF₄), as catalysts. The aza-Michael products have been targeted as truncated ritonavir analogues for investigation as potential HIV -1 protease inhibitors, and representative compounds have been subjected to enzyme inhibition assays to explore the extent and type of inhibition. Lineweaver-Burk and Dixon plots have indicated competitive inhibition in one case as well as non-competitive inhibition in another, and the inhibition constants (Ki) have been compared with that of the ritonavir. Computer modelling studies have also been conducted on selected chromonecontaining derivatives, using the ACCELRYS Cerius² platform. Interactive docking of the chromone-containing ligands into the HIV -1 protease receptor site, using the Ligandfit module, has indicated the importance of hydrogen-bonding interactions mediated by bridging water molecules situated in the receptor cavity. NMR spectroscopy has been used to elucidate complex and competing mechanistic pathways involved in the Baylis-Hillman reactions of selected 2-nitrobenzaldehydes with MVK in the presence of DABCO - reactions which afford the normal BaylisHillman product, the MVK dimer and syn- and anti-Baylis-Hillman type diadducts. The kinetic data confirm the concomitant operation of two pathways and reveal that, in the initial stage of the reaction, the product distribution is kinetically controlled, whereas in the latter stage, thermodynamic control results in the consumption of the normal Baylis-Hillman product and predominance of the anti-diadduct.
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Studies in marine diterpene chemistry
- Authors: Van Wyk, Albert Wynand Wincke
- Date: 2008
- Subjects: Natural products Diterpenes Mollusks Marine metabolites Chemical oceanography
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4354 , http://hdl.handle.net/10962/d1005019
- Description: This thesis comprises both a natural product investigation and a synthetic component. The natural product investigations are presented in Chapters Two and Three. In Chapter Two the isolation and spectroscopic identification of the new isocopalane diterpene 12S,13R,14Sisocopalan- 13-ol-12,14-diacetate (2.1) and two known 3-(14S)-isocopal-12-ene-15-oyl-1- acetyl-sn-glycerol (2.2) and 3-(14S)-isocopal-12-ene-15-oyl-2-acetyl-sn-glycerol (2.3) from a single, large, unidentified sub-Antarctic nudibranch, collected near Marion Island, approximately 2000 km south of Cape Town are described. Chapter Three discusses the isolation, spectroscopic structure elucidation and anti-oesophageal cancer activity (3.1-3.4 only) of two known labdane diterpenes 6β,7α-diacetoxylabda-8,13E-dien-15-ol (3.1) and 2α,6β,7α-triacetoxylabda-8,13E-dien-15-ol (3.2) and one new 6β,7α,15-triacetoxylabda 8,13E-diene (3.3), as well as new 3α,11-dihydroxy-9,11-seco-cholest-4,7-dien-6,9-dione (3.4) and cholest 7-en-3,5,7-triol (3.5) from the endemic pulmonate mollusc, Trimusculus costatus. The absolute configuration of 3.2, and hence 3.1 and 3.3 (from biogenetic arguments) was determined through X-ray diffraction of a single crystal of the camphanate ester of 3.2. The absolute configuration of the secondary hydroxyl at C-3 of 3.4 was established using the Modified Mosher’s method. The synthetic component of the thesis commences in Chapter Four with the semi-synthesis of labdane diterpene nitriles 9α-cyano-15,16-epoxy-7β-hydroxylabda-13(16),14-dien-6-one (4.1), 9α-cyano-15,16-epoxy-7-hydroxylabda-7,13(16),14-trien-6-one (4.2) and 9α-cyano-15,16- epoxy-6β,7β dihydroxylabda-13(16),14-diene (4.3) from the terrestrial labdane diterpene, hispanolone (4.4). This work is an extension of previous synthetic studies directed towards the synthesis of T. costatus metabolites. Diterpenes 4.1-4.3 exhibited in planta activity against the economically important crop pathogens, Magnaporthea grisea and Puccinia recondita. Chapter Five describes the successful semi-synthesis of two isomeric marine molluscan labdane diterpene aldehyde metabolites, labd-13E-ene-8β-ol-15-al (5.1) and labd-13Z-ene- 8β-ol-15-al (5.2) from the commercially available, terrestrial plant derived, labdane diterpene manool (5.3). Diterpenes 5.1 and 5.2, originally isolated from the Mediterranean nudibranch,Pleurobranchaea meckelii and selected diterpenes arising from this synthesis were evaluated for their activity against an oesophageal cancer cell line (WHCO1). Chapter Six further develops the research discussed in Chapter Five, where ethyl 17-norabiet-13(15)-E-en-8β-ol- 16-oate (5.49) and ethyl 17-norabiet-13(15)-Z-en-8β-ol-16-oate (5.50) were first semisynthesized serendipitously. Based on their structural relationship to naturally occurring tricyclic diterpenes with anti-plasmodial activity, tricyclic diterpenes, 17-norpimaran-13α- ethoxy-8,16-olactone (6.6), 17-norisopimar-15-ene-8β,13β-diol (6.7), 17-norisopimarane- 8β,16-diol (6.8) and 17-norabiet-13(15)-ene-8β,16-diol (6.9) were semi-synthesized from the terrestrial labdane diterpene, 5.3, and critically evaluated for their antimalarial potential from parasite inhibition and haemolytic studies.
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