An experimental and theoretical investigation of unstable Fischer chromium carbene complexes
- Authors: Makanjee, Che Azad
- Date: 2013 , 2013-03-27
- Subjects: Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4284 , http://hdl.handle.net/10962/d1002953 , Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Description: This organometallic study involves the use organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are typically electrophilic and are stabilized by a single π-donor substituent, and contain low oxidation state metals (often but not always from Group 6). They are highly reactive and can give access to a range of biologically active compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and characterization of three MOM-protected α-alkoxy organostannanes was successfully carried out via a nucleophilic addition of tributylstannyllithium to suitable aldehydes, and immediate protection of the alcohol with MOM. Two N-BOC protected α-amino organostannanes were successfully synthesized and characterized via α-lithiation and tin-lithium exchange in the presence of TMEDA. Tin-lithium transmetallation of the organostannanes allowed access to the organolithiums required for the synthesis of novel Fischer carbenes. Addition of chromium hexacarbonyl to the organolithiums formed the acylpentacarbonyl chromate salt which was alkylated with Meerwein salt, resulting in the Fischer carbene and a by-product, tetrabutyltin, which proved difficult to remove. Several Fischer carbenes were synthesized and characterized, some simple and known and some novel. In silico work explored the reaction coordinate of the [2+2] cycloaddition towards the formation of β-lactams, and the photoactivation cycle that precedes this process. Computational work also showed the effect of the ligand on the stability and reactivity of the carbene. It was found that in some cases the oxygen on the ligand could negatively influence the stability of the carbene (when compared to a simple methyl carbene). A link between bond orders and back donation in Fischer carbenes was explored in an attempt to theoretically predict the stability of a range of carbenes. , Microsoft� Office Word 2007
- Full Text:
- Date Issued: 2013
Spatio-temporal dynamics of ichthyoplankton in the Kowie estuary, South Africa
- Authors: Kruger, Michelle
- Date: 2010
- Subjects: Fishes -- Larvae -- South Africa -- Port Alfred , Estuarine fishes -- South Africa -- Port Alfred
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5319 , http://hdl.handle.net/10962/d1005164 , Fishes -- Larvae -- South Africa -- Port Alfred , Estuarine fishes -- South Africa -- Port Alfred
- Description: Ichthyoplankton dynamics in the permanently open Kowie Estuary, in the warm temperate region of South Africa was investigated. The composition, abundance, distribution and seasonality of larval fishes were studied over a two year period between 2004 and 2006. Additionally, tidal exchange of ichthyoplankton and the use of frontal zones in the mouth region of the estuary were also explored between 2008 and 2009. Temporal and spatial trends in occurrence of larval fishes within the estuary and associated marina were obtained from data collected seasonally using boat-based plankton netting at 14 sampling stations along the length of the estuary. A total of 11 128 larval fishes were collected, representing 23 families and 38 taxa. Clupeidae and Gobiidae were the dominant fish families, contributing 47.0 % and 24.7 % respectively to the total catch. Estuarine resident species dominated the overall catch (91 %). A notable absence of older stage larvae and early juveniles characterised the artificial channels of the marina and estuary mouth region. This was attributed to the absence of a shallow, marginal water habitat typical of successful estuarine nursery areas. Tidal exchange of larval fishes was investigated in the Kowie Estuary using a new technique. A set of drifting light traps were set repetitively on the ebb and flood tide every second night for two consecutive 14 day periods during the peak estuarine recruitment period. A total of 553 larval fishes were caught during the study, representing nine families and 26 species. Blenniidae and Clupeidae dominated the catches. Family and species occurrence changed with tide state. Species richness (d) and diversity (H’) varied with tide and was highest on flood tides. Estuary-dependent species, such as Omobranchus woodii were more dominant on flood tides, whilst larvae of marine-spawned species, such as Sardinops sagax, were dominant on the ebb tide. Light trap catches yielded a different composition in terms of development stage / size and species, when compared to towed net studies. Towed plankton nets were again used to study the shear fronts that characterise the mouth region of the canalised Kowie Estuary. It was hypothesised that the convergence zone of the front provides feeding opportunities for ichthyoplankton. Ichthyoplankton, zooplankton and phytoplankton was collected from within and immediately outside of the convergence zone during frontal conditions. Species specific distribution trends emerged from this study. Postflexion larvae and early juvenile stages of the estuary dependent Mugilidae were only present in the foam line of the convergence zones. Some known predators of ichthyoplankton were also present in slightly higher numbers in the convergence zone (isopods) while other predators such as mysid shrimps, chaetognaths and cnidarians were more abundant out of the convergence zone. It appears that these zones may provide access to temporary food patches in the lower estuary but will be accompanied by a trade-off with increased isopod predators. The Kowie Estuary is a heavily impacted system and lack of adequate freshwater supply; artificial channelling and pollution ultimately have a negative impact of the success of this system as a nursery area. Rehabilitation of marginal areas in the lower estuary and marina is suggested as remedial action to re-establish the integrity of the nursery function this system could offer.
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- Date Issued: 2010
Statistical analyses of artificial waterpoints: their effect on the herbaceous and woody structure composition within the Kruger National Park
- Authors: Goodall, Victoria Lucy
- Date: 2007
- Subjects: South African National Parks , Ecology -- Statistical methods , Regression analysis , Log-linear models , Game reserves -- South Africa , Kruger National Park (South Africa)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5570 , http://hdl.handle.net/10962/d1002810 , South African National Parks , Ecology -- Statistical methods , Regression analysis , Log-linear models , Game reserves -- South Africa , Kruger National Park (South Africa)
- Description: The objective of this project is to link the statistical theory used in the ecological sciences with an actual project that was developed for the South African National Parks Scientific Services. It investigates the changes that have occurred in the herbaceous and woody structure due to the closure of artificial waterpoints; including the impacts that elephants and other herbivores have on the vegetation of the Kruger National Park. This project was designed in conjunction with South African National Parks (SANP) Scientific Services and it is a registered project with this department. The results of this project will be submitted to Scientific Services in accordance with the terms and conditions of a SANP research project. A major concern within the KNP is the declining numbers of rare antelope and numerous projects have been developed to investigate possible ways of halting this decline and thus protecting the heterogeneity of the Kruger National Park. Three different datasets were investigated, covering three aspects of vegetation structure and composition within the KNP. The first investigated the changes that have occurred since the N'washitsumbe enclosure in the Far Northern KNP was fenced off from the rest of the park. The results show that over the 40 years since the enclosure was built, changes have occurred which have resulted in a significant difference in the abundance of Increaser 2 and Decreaser grass species between the inside and the outside of the enclosure. Increaser 2 and Decreaser categories are the result of a grass species classification depending on whether the species thrives or is depressed by heavy grazing. The difference in grass species composition and structure between the inside and the outside of the enclosure indicates that the grazing animals within the KNP have influenced the grass composition in a way that favours the dominant animals. This has resulted in a declining roan antelope population - one of the species that is considered as a 'rare antelope'. Many artificial waterpoints (boreholes and dams) have also been closed throughout the KNP in the hope of resulting in a change in vegetation structure and composition in favour of the roan. Veld condition assessment data for 87 boreholes throughout the Park was analyzed to determine whether the veld in the vicinity is beginning to change towards a more Decreaser dominated sward which would favour the roan. The results were analyzed for the different regions of the Park; and they indicate that changes are becoming evident; however, the results are not particularly conclusive, yet. The majority of the boreholes were closed between 1994 and 1998 which means that not a lot of data were available to be analyzed. A similar study conducted in another 10 years time might reveal more meaningful results. However the results are moving in the direction hoped for by the management of the KNP. The results show that the grass composition has a higher proportion of Decreaser grasses since the closure of the waterpoints, and the grass biomass around these areas has also improved. The results were analyzed on an individual basis; and then on a regional basis as the minimal data meant that the individual analyses did not provide any significant results. A third study was then done on the impact that the rapidly increasing elephant population on the vegetation within the Riparian zone along three rivers in the Far Northern region of the KNP. The riparian zone is an important part of the landscape, in terms of providing food for many animals as well as shade. The elephant population has increased substantially since the termination of the culling program and this means that the feeding requirements of the population has increased which could result in severe damage upon the vegetation, as elephants can be very destructive feeders. The results show surprising differences between the three years of data that were analyzed; however the results indicate that the elephants are targeting specific height ranges of trees when feeding; however they do not seem to consistently target specific tree species. This is positive for the diversity of the Riparian zone as this region is very important both ecologically and aesthetically for the tourists who visit the Park.
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- Date Issued: 2007
"From the inside": how to attribute emotions to others
- Authors: Mitova, Velislava Atanasova
- Date: 2003
- Subjects: Emotions (Philosophy) , Theory (Philosophy)
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2741 , http://hdl.handle.net/10962/d1007661 , Emotions (Philosophy) , Theory (Philosophy)
- Description: I argue that a specific version of Theory theory is necessary and sufficient for attributions and predictions of others' emotions. Theory theory is the view that we attribute and predict others' mental states on the basis of a (tacit) body of generalisations about mental states, their situational input, and behavioural output. Theory's antagonist, Simulation theory, is the view that we ascribe mental states to others by simulating - or running ' off-line ' - their doxastic, emotional, and contextual situations. My argument for Theory's necessity and sufficiency develops in three stages: First, I show that some version of Theory is necessary for predictions of all mental states on the basis of the ascriber's knowledge of the subject's other mental states. The linchpin of the arguments here consists of considerations from relevant similarity between the ascriber's and the subject's mental states. Simulation cannot provide criteria for such similarity, and so, I argue, predictions must advert to Theory. Second, I develop a sui generis model of emotions, according to which (i) emoticns' necessary objects and typical causes are concern-based construals; and (ii) emotions qua attitudes are (a) complex states embedded in a narrative structure, (b) characterised in terms of their object, their expressive behaviour, and their phenomenology. Third, I show that, considering the nature of the objects of emotions, some Theory is necessary for emotion-predictions and -attributions. Moreover, I develop a version of Theory, based on my analysis of emotions and narrative structures, and argue that this version of Theory is both necessary and sufficient for emotion-predictions and -attributions.
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- Date Issued: 2003
Methods for designing and optimizing fuzzy controllers
- Authors: Swartz, Andre Michael
- Date: 2000
- Subjects: Fuzzy sets , Fuzzy systems , Automatic control
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5412 , http://hdl.handle.net/10962/d1005226 , Fuzzy sets , Fuzzy systems , Automatic control
- Description: We start by discussing fuzzy sets and the algebra of fuzzy sets. We consider some properties of fuzzy modeling tools. This is followed by considering the Mamdani and Sugeno models for designing fuzzy controllers. Various methods for using sets of data for desining controllers are discussed. This is followed by a chapter illustrating the use of genetic algorithms in designing and optimizing fuzzy controllers.Finally we look at some previous applications of fuzzy control in telecommunication networks, and illustrate a simple application that was developed as part of the present work.
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- Date Issued: 2000
An investigation of nondeterminism in functional programming languages
- Authors: Graham, Gwyneth Clare
- Date: 1997
- Subjects: Functional programming languages
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4658 , http://hdl.handle.net/10962/d1006658 , Functional programming languages
- Description: This thesis investigates nondeterminism in functional programming languages. To establish a precise understanding of nondeterministic language properties, Sondergaard and Sestoft's analysis and definitions of functional language properties are adopted as are the characterizations of weak and strong nondeterminism. This groundwork is followed by a denotational semantic description of a nondeterministic language (suggested by Sondergaard and Sestoft). In this manner, a precise characterization of the effects of strong nondeterminism is developed. Methods used to hide nondeterminism to in order to overcome or sidestep the problem of strong nondeterminism in pure functional languages are defined. These different techniques ensure that functional languages remain pure but also include some of the advantages of nondeterminism. Lastly, this discussion of nondeterminism is applied to the area of functional parallel language implementation to indicate that the related problem and the possible solutions are not purely academic. This application gives rise to an interesting discussion on optimization of list parallelism. This technique relies on the ability to decide when a bag may be used instead of a list.
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- Date Issued: 1997
A life-history approach to the early ontogeny of Oreochromis Mossambicus (Peters)
- Authors: Holden, Kathleen Karen
- Date: 1991
- Subjects: Cichlids -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5298 , http://hdl.handle.net/10962/d1005143 , Cichlids -- Research
- Description: The adult ecophenotype of an animal is the result of interactive events which occur during its early ontogeny through a series of sequential steps of increasing morphological complexity. At the step boundaries, there are qualitative and quantitative changes in the structures present which will allow the developing animal to successfully cope with new trophic features of its internal and external environment. There is some controversy as to whether the shifts that occur at these step boundaries are gradual or saltatory. Environmental parameters, early life-history plasticity and genetic instructions are the interactive events which produce the ecophenotype. The early ontogeny of Oreochromis mossambicus was followed from the time of egg activation until juvenilization. The eggs, embryos and larvae were artificially incubated at 25±0.5ºC. The descriptive text and the figures are composites derived from drawings, photomicrographs and observational notes of live and preserved individuals. It was found that the early ontogeny of O. mossambicus consists of an embryonic period of approximately 11 days and a truncated larval period of about 4-5 days. The embryonic period can be further divided into a cleavage, an embryonic and a free-embryonic phase. Comparisons of the early development of three other mouthbrooding and one substrate-spawning cichlid done by other researchers, revealed that the early ontogeny of O. mossambicus closely resembles that of Sarotherodon melanotheron (also a mouthbrooding species). Embryo length and yolksac area changed gradually in the cleavage and embryonic phases, showed little or no change in the free-embryonic phase, and changed rapidly in the larval period. Heart rate increased gradually in the embryonic phase and peaked just before the shift into the free-embryonic phase. Gradual decrease in heart rate occurred in the free-embryonic phase followed by a second peak at the boundary between the embryonic and larval periods. In the larval period, heart rate levelled off. Although distinctive boundaries were not clearly evident at all steps, it was concluded that there are three definite ontogenetic steps which occur at the boundaries between the embryonic phase, the free-embryonic phase and the larval period. These thresholds occur at a point where shifts in the trophic features of the external environment are expected. Regression analysis revealed that two regimes exist for changes in embryo length and yolksac area and that a breakpoint occurs just prior to the boundary between the embryonic and larval periods. It appears that ontogeny is saltatory at points where a change in the trophic features of the environment requires a new set of interactions to occur between the environment and the ecomorphological and eco-ethological features of the animal.
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- Date Issued: 1991
The petrology of the basalts of the Dordabis Formation in the vicinity of Dordabis in central S.W.A./Namibia|
- Authors: Williams-Jones, Ian Eric
- Date: 1985 , 2013-03-14
- Subjects: Basalt -- Namibia , Petrology -- Namibia , Geochemistry -- Namibia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5062 , http://hdl.handle.net/10962/d1013277
- Description: The late Proterozoic volcanic and sedimentary sequence in the Dordabis area SWA/Namibia has been named the Dordabis Formation and subdivided, on the basis of field, petrological and petrographic evidence, into the Opdam and Bitterwater Members. Relict phases including augite and minor plagioclase only occur in the Bitterwater metalavas, as recrystallisation is complete in the Opdam metal avas. The composition of the relict feldspars ranges from labradorite in the ophitic basalts to oligoclase in the blastoporphyritic metalavas. The feldspars in the Opdam member are albitic in composition (An content 0,0 to 1,7) . Epidote compositions are typical of those occurring in metabasic rocks. Samples with high-iron whole-rock compositions are accompanied by high concentrations of Fe3+ in concomitant epidotes. Sixty three samples were analysed using X-ray fluorescence spectrometry to determine concentrations of major and 16 trace elements. Although greenschist facies metamorphism, metasomatism and shearing have produced scatter in the more mobile element concentrations, variation trends in other elements closely resemble modelled low-pressure fractional crystallisation trends. The Dordabis metalavas are petrologically classified as sub-alkaline, tholeiitic continental basalts. Low K/Rb ratios and low ratios of less incompatible to more incompatible elements probably reflect a source that has either been metasomati ca lly enriched or that has undergone little previous partial melting. Overlapping whole-rock variation trends indicate that the generally more evolved Opdam and primitive tholeiitic Bittenwater lavas are cogenetic. A comparison of the Dordabis Formation with the Sinclair Sequence and the Koras Group shows that their ages, petrology, petrography, associ a ted sedimentary suites and depositional environments are similar. It is concluded that they may possibly be coeval equivalents.
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- Date Issued: 1985