Masters Degrees (Chemistry)

Permanent URI for this collectionhttps://hdl.handle.net/10413/6597

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A detailed kinetic and mechanistic investigation into the rate of chloride substitution from chloro terpyridine platinum (II) and analogous complexes by a series of azole nucleophiles.
(2010) Gillham, Kate J.; Reddy, Desigan.; Jaganyi, Deogratius.
Progress towards the synthesis of Indolizidine alkaloid 223AB
(2008) Janse van Rensburg, Caryl Kerith Alice.
It has been shown that alkaloids from various sources are vital as lead compounds in medicinal research and thus also the efficient synthesis of these. With the goal of developing a general synthetic route that can potentially access pyrrolizidine, indolizidine, quinolizidine and possibly lehmizidine alkaloid skeletons, a modified route that has been shown to produce pyrrolizidines was employed towards the synthesis of indolizidine alkaloid 223AB. Within this synthesis, a 6-endo-dig hydroamination-cyclization step was attempted for construction of the bicyclic system. For this purpose, a selection of titanium-based catalysts were synthesized in order to determine their regiochemical outcome. For the purpose of investigating ab initio the mechanism of regioselective hydroamination, the skills and methods involved in computational chemistry were acquired through a study into amide rotational barriers: A range of novel 2-oxo-2H-chromen-7-yl dimethylcarbamates were synthesised containing either an oxygen or sulphur in the α-position to the carbonyl or thiocarbonyl group of the amide moiety. Microwave synthesis was essential for the successful synthesis of some of the sulphur containing carbamates. The barriers to internal rotation of each of these compounds were investigated as follows. Variable Temperature and Exchange Spectroscopy NMR was performed on these compounds and the barrier to free amide rotation was calculated. Each of these compounds were also modeled ab initio and the gas phase barrier to rotation calculated. These three sets of data were compared and the influence of the α-heteroatom on rotation for amides and thioamides evaluated.
Structural and Physical Studies of Co(III) Salen Derivatives.
(2007) Govender, Santham.
A number of ligands that belong to the salen-type family were synthesized in this thesis. These ligands were synthesized from salicylaldehyde and 1,2-phenylenediamine, 1,3- diamino-2-hydroxypropane, 1,2-diamino-ethane, N-(3-aminopropyl)-1,3-propanediamine, diethylenetriamine, diaminomaleonitrile, 2,2-dimethyl-1,3-propanediamine and 1,3- diaminopropane. From this range of ligands, H2salophen was chosen as the ligand for further studies. This work is aimed primarily at elucidating the structures and spectroscopic properties of [Co(salophen)(amine)2](OAc) derivatives, where salophen is N,N’-disalicylidene-1,2- phenylenediamine and the amines used were butylamine, benzylamine, a- methylbenzylamine, dibutylamine, N-methylpiperazine and piperidine. Three novel crystal structures of [CoIII(salophen)L2]Cl derivatives, where L = butylamine, benzylamine, and piperidine, with Co-N distances that range from 1.901 Å to 2.024 Å, have been reported in this thesis. The novel crystal structure of [Co(salophen)(N-MePipz)(OAc)] is also reported in this thesis. These cobalt complexes have been analysed by 1H, 13C and 59Co NMR as well as electronic and IR spectroscopy. A 59Co NMR spectrum was obtained for the [Co(salophen)(BuNH2)2]CH2Cl2×Cl complex. The spectrum exhibits a single line at 8504 ppm. The binding constants of all [Co(salophen)(amine)2](OAc) complexes, where amine = butylamine, benzylamine, a-methylbenzylamine, dibutylamine, N-methylpiperazine and piperidine, were determined by spectroscopic titrations. The titrations were carried out at various concentrations of the amine and at temperatures ranging from 25°C to 45°C. It was found that the primary amines had much larger values of K1 and K2 compared to the secondary amines. Typical values of K1 and K2 were 8000 M-1 and 63.6 M-1 respectively at 25°C, for a-methylbenzylamine. Of the primary amines, it was found that a- methylbenzylamine had the largest value of K1 and K2 compared to the other two amines. For the secondary amines, it was found that N-methylpiperazine had the bigger value of K1 compared to that of dibutylamine.
Elemental distribution in selected edible nuts and the impact of soil quality on the chemical characteristics of macadamia (Macadamia integrifolia) nuts
(2007) Moodley, Roshila.
Environmental and nutritional imperatives make it necessary to carry out regular and reliable
Synthesis of novel pentacyclo-undecane chiral ligands for application in asymmetric catalysis
(2008) Naicker, Tricia.
There is enormous interest in the design and development of efficient chiral ligands for asymmetric catalysis, as a result, this field has become one of the most popular areas of research in organic chemistry. This project involved the investigation of the novel chiral pentacyclo-undecane (PCU) diol 54a, PCU bisimine 87 and PCU bis(oxazoline) 100 type ligands. The PCU diol ligand was synthesized, but proved to be difficult to obtain enantiomerically pure which hindered further investigation into this type of ligand. The PCU bisimine ligand 87 was synthesized. However due to its instability it was not further pursued. Synthesis of the PCU bis(oxazoline) ligand 100 was successful. This ligand was complexed to various metal salts and its efficiency as a chiral Lewis acid catalyst was evaluated on the asymmetric Diels-Alder reaction between 3-acryloyloxazolidin- 2-one 52 and cyclopentadiene 33. The anhydrous magnesium perchlorate ligand complex emerged as the best catalyst providing the endo-cycloadduct product 53 in 81 % enantiomeric excess at -40 oC. Optimizations of the possible conformations of the magnesium complex of ligand 100 with the substrate 52 were performed using Density Functional Theory (DFT) calculations. The more energetically favoured complex conformation was established. The Re-face of the dienophile which was less hindered produced the product consistent with the experimentally observed product 16. Based on the calculated bond lengths from the computational model binding of the ether oxygen on the PCU moiety to magnesium was observed. All the novel compounds were fully characterized using NMR, IR and mass spectroscopy as the main tools.
N-butane activation over ruthenium and iron promoted VPO catalysts.
(2009) Masilo, Neoentle.; Friedrich, Holger Bernhard.
The Fe- and Ru-promoted vanadium phosphorus oxide (VPO) catalysts were synthesized via the organic route in iso-butanol to form the VPO precursor, VOHPO4·0.5H2O. The resulting precursor was then activated in a stream of nitrogen to form an amorphous (VO)2P2O7, which crystallized after conditioning in the reactor in the presence of n-butane. The promoted catalysts were synthesized at 0.1%, 0.3% and 1% loading, pelletized and sieved to give a 300-600 μm pellet size. The catalysts were tested in a fixed-bed continuous flow micro-reactor and the products were analyzed by GC’s equipped with a flame ionization detector (FID) to monitor maleic anhydride and n-butane and a thermal conductivity detector (TCD) to monitor the carbon oxides. A range of characterization techniques were employed to determine the influence of the promoting elements on a VPO catalyst and to associate the composition of the catalysts obtained from such techniques with their performance. The characterization techniques used include X-ray diffraction (XRD), BET-surface area, ICP-OES, EDS, 31PNMR, TPR, redox titrations, ATR and SEM to determine the phase composition of the catalysts, the surface area of the promoted catalysts relative to the un-promoted VPO, elemental mole ratios, the reducibility of the catalysts, average vanadium oxidation state, determination of the anions present in the surface of the catalysts and the variations in the morphology of the catalysts, respectively. Optimization of the system involved variation of the GHSV, the reactor temperature and the promoter loading. (Activation of a 0.75% n-butane in air mixture was performed at an optimum temperature of 400oC while varying the gas hourly space velocity to establish a range of feed conversions and subsequently determine the activity of each catalyst with respect to n-butane conversion). The promoted catalysts modified the morphology of the catalysts as evidenced by the scanning electron microscopy and the X-ray diffraction patterns. Furthermore an improved conversion was obtained with these catalysts. However, only the 0.1% iron-promoted catalyst improved maleic anhydride yield leading to ca. 10% maleic anhydride yield increment. Yields of 46% and 55% were obtained at GHSVs of 2573 and 1450 per hour respectively and a temperature of 400oC. Electronic and structural modifications were encountered leading to an improved catalytic performance. The performance of this catalyst is associated with a vanadyl pyrophosphate phase (XRD), and a limited and controlled amount of V5+ species as illustrated in the TPR, and solid state 31P NMR data. Moreover, this modification can be considered both structural and electronic in nature as observed in the SEM images and FTIR spectra of this catalyst. Furthermore, this improved performance is possible at higher conversions 80 to 90% conversion.
An investigation into the antimalarial activity of metal chelators
(2008) Pareskevopoulos, Jason Nicholas.; Maguire, Glenn Eamonn Mitchel.; Kruger, Hendrik Gerhardus.
Malaria remains one of the greatest problems facing developing nations, especially in sub-Saharan Africa. Part of the problem stems from increased resistance to current treatments hence there is a large drive to develop novel antimalarial compounds. Several chelating compounds, including 8-hydroxyquinoline (8-HQ), 1,10- phenanthroline (1,10-phen) and 2,2.6,2-terpyridine (terpy), have disputed activities (8-HQ and 1,10-phen) or are untested (terpy). Furthermore the mechanism(s) by which these ligands and/or their complexes with metal ions exhibit their toxic effect is unknown. In order to resolve these issues, a study of the antimalarial activities of the free ligands, the ligands complexed with metal ions (Au 3+, Cu 2+, Fe 3+, Pd 2+ and Pt 2+), and the ligands with free metals in solution were measured. The ligands, complexes and metals were also tested for their ability to inhibit β-haematin formation, the mode of action ascribed to the most widely used antimalarial, chloroquine. The background toxicity levels of the various metal ions (previously unreported) were also measured and are reported here. None of the ligands were found to have particularly high activity (all approximately 1μM). In general the metals in were found to have no beneficial effect on activity whether complexed or freely available in solution. None of the ligands were found to inhibit β-haematin formation. The complexes however, with the exception of those of Cu 2+, all inhibited β-haematin formation. Upon further investigation it was found that the each of the metal ions with the exception of Cu 2+ had an innate ability to inhibit β-haematin formation. Thus the mode of action of the ligands and the complexes is likely to be via different mechanisms. In an attempt to enhance the activities of the ligands they were modified by covalently linking them to nutrients essential to the malaria parasite (adenosine and pantothenic acid). These six novel compounds however, showed no improvement in action.
Studies on ozone initiated inactivation of pathogenic bacteria in aqueous systems
(2008) Zuma, Favourite N.
The effect of ozone on the inactivation of two Gram-negative strains (Escherichia coli and Pseudomonas aeruginosa) and one Gram-positive endospore (Bacillus subtilis) bacteria, often present in water and the cause of some waterborne diseases was investigated as a function of ozone concentration and ozonation duration. Ozone was generated in situ using corona discharge methods where the ozone concentration ranged from 0.906 - 4.724 mg/L and the inactivation of the three microbes followed pseudo-first order kinetics with respect to the microbes. Three microbes were cultured and the influence of temperature and pH of the aqueous systems on the ozone initiated inactivation rate of the three microbes was also investigated. This study reports that molecular ozone is more effective than hydroxyl radicals initiated by the ozone chain reactions. Two suggested mechanisms for the antimicrobial effectiveness of ozone in water systems from the literature is discussed. The study also found that ozonation significantly decreased the Biological Oxygen Demand (BOD) value of natural water.
Synthesis of polycyclic hydantoin derivitaves and peptides.
(2008) Albasheer, Mohamed Saadaldin Altaib.; Govender, Thavendran.; Kruger, Hendrik Gerhardus.
Cyclic cage compounds have attracted much attention in pharmaceutical studies. The lipophilic nature of these compounds plays an important role in facilitating the crossing of the cellular membranes, including the blood brain barrier (BBB) and the central nervous system (CNS). Several adamantane and pentacyclo[5.4.0.02,6.03,10.05,9]undecane (PCU) derivatives have shown great potential as antiviral, antibacterial and neuroprotective compounds. The aim of this study includes the synthesis of hydantoin derivatives of adamantane and PCU as anticonvulsant compounds. Fosphentoin sodium (Cerebyx) 48 is a commercial anticonvulsant drug. Structurally, compound 51 and 52 are similar to Cerebyx 48, where the two phenyl groups have been replaced with PCU or adamantane skeleton respectively. The cage skeleton should increase the lipophilic character of the drug whilst the phosphate group should retain the water solubility of the substrate. The attempted synthesis of these compounds is described in Chapter 2. The PCU hydantoin is readily converted to the PCU amino acid. The synthesis of the PCU amino acid 41 and its Fmoc derivative 106 is described in Chapter 3. This compound was incorporated into small peptides, namely Ala-Ala-Ala-PCU-Ala-Ala-Ala-Fmoc and Ala-Val- PCU-Ile for future testing as a potential anti-cancer agent. NMR studies of these peptides are also reported.
Synthesis and incorporation of a Trishomocubane Amino Acid into short Peptides
(2006) Jali, Samuel.
Cage compounds have attracted pharmaceutical and biological interest amongst others as anti-Parkinson agents. The serendipitous observation of the activity of 1-aminoadamantane 1 in Parkinsonian patients against selected viruses i.e. Herpes simplex Type I & II and Influenza A2-Asian viruses/Taiwan has increased the interest in cage compounds. This study involves the synthesis of the cage amino acid 14. Due to the insolubility of pentacyclo-[6.3.0.02,6.03,10.05,9]-undecane (trishomocubane) amino acid 14 in both polar and nonpolar solvents, including DMSO (d6), the synthesis of Fmoc-tris amino acid 50 was required for analysis. The Fmoc derivative of trishomocubane amino acid was also useful for controlled* coupling of the cage amino acid 14 to short peptides. The synthesis of the Fmoc-tris amino acid fluoride derivative is described as well as that of the tri-peptide (Ala-Ala-Ala). The incorporation of the Fmoc-tris amino acid fluoride in a tetra-peptide Ala-Ala-Ala-tris and in a hepta-peptide Ala-Ala-Ala-tris-Ala-Ala-Ala will also be presented. A computational chemistry project was undertaken using density functional theory (B3LYP) at the 6-31+G(d) level of theory, so as to enhance the understanding of the mechanism of esterification. Methanol, acetyl chloride and acetic acid were used in the model for simplicity. Four membered ring transition states were obtained with both acetyl chloride and acetic acid. A six membered ring transition state is facilitated by the selective use of one methanol molecule from the solvent. Both a concerted and step-wise mechanism are presented.
Structure and synthesis of Phloroglucinol derivatives from Hypericum roeperianum
(2010) Smith, Kerry-Ann
The research presented in this study combines natural product chemistry with organic
Application of analytical chemistry and waste minimisation techniques in a paint drier plant.
(2009) Rasalanavho, Muvhango
Environmental sustainability, strict Municipal bylaws, ever-increasing waste disposal
Bioactive sesquiterpenoids from dicoma anomala subsp. gerrardii
(2008) Van der Merwe, Marina Mikhailovna.; Van Heerden, Fanie Retief.; Parkinson, Chris.
Through South Africa’s first collaborative project between a large scientific organisation, the Council for Scientific and Indust rial Research (CSIR), and the Traditional Healer’s Committee, Dicoma anomala was identified as a plant containing potent anticancer and antimalarial compo unds. In the process of evaluation, extracted plant material with reported or anecdotal use for the treatment of respiratory problems was found to have significant anticancer activity in vitro in a 3-cell line preliminary screen . The extract was further shown to have potent anticancer activity against the 60-cell line panel at the National Cancer Institute (NCI) in the USA. Bioassay-guided fractio nation, initially utilising an in vitro anticancer assay, and structural elucidation resul ted in two potent compounds with sesquiterpenoid skeletons (C-15 and C-30). The crystal structure of the C-15 compound, not published previously, was obtained. B oth compounds were further screened in an antiplasmodial assay during the cour se of the National Drug Development Platform (RSA: CSIR, MRC and UCT) proje ct, and were found to have potent activity against Plasmodium falciparum (a malaria protozoon). Although the C-15 compound had a selectivity index (SI) of 10, suggesting that it was suitable for subsequent development, the dimer was highly toxic (SI index of 1), limiting opportunities for future development. A further study of the structure- activity relationship (SAR), which was initiated fo r the C-15 compound, showed that removal of each unsaturated structural compone nt decreased activity 10–fold in both bioassays. Additional investigations were c arried out into amino-acid Michael adducts with the exocyclic double bond of t he C-15 sesquiterpenoids, and the products were characterised by NMR spectroscopy and mass spectrometry. A similar investigation, involving the conjugate addi tion of simple amines, was undertaken in an attempt to enhance the bioavailabi lity of the parent sesquiterpenoid. Three diethylamine derivatives wer e prepared and characterised. A general 10-fold drop in the bioactivity of these “pro-drug” derivatives in both assays was observed. Finally, the C-15 compound was tested in vivo in the Plasmodium berghei murine malaria model and was found to have some eff ect on the survival rates of the laboratory animals when c ompared with the control. A possible mode of action is suggested based on the e xperimental and published bioactivity data. Further studies to improve the bi oactivity and alternative design of future in vivo studies are also proposed.
Isolation and characterisation of antibacterial agents produced by soil bacterium V3.
(2006) Khumalo, Lindiwe Lucia.
Actinomycetes are bacteria belonging to the order of Actinomyceteles and are
A comparative study of mixed metal oxide catalysts for the oxidation of C4, C6 and C8 linear alkanes.
(2007) Govender, Nishlan.
The Fischer-Tropsch process in South Africa, used for producing chemicals from synthesis gas, which is mostly derived from the gasification of coal, gives a large amount of medium chain length alkanes (C4-C8), which have little commercial value. Internationally, industry has recently placed more focus on the conversion of alkanes to value-added products. Two important routes to achieving this are dehydrogenation and oxidative dehydrogenation. The latter is an economically feasible route, in which there is growing interest by the international research community, and was investigated in this study.
Towards novel Au (III) porphyrins : synthesis and characterization of a range of mesotetraalkylporphyrins.
(2007) Salmond, Rosanne C.
The principal goal of this work was to synthesize and fully characterize a range of free
A chemical and pharmacological investigation of three South African plants.
(2006) Khorombi, Tendani Eric.
Three plant species (Phylica paniculata Willd., Pergularia daemia Forssk. and Monsonia
A theoretical investigation of the resolution of chiral amines via chiral macrocycles and the synthesis of some macrocyclic precursors.
(2006) Ramdhani, Reshika.
No abstract available.
A phytochemical study of Schefflera umbellifera and Elephantorrhiza elephantina.
(2007) Mthembu, Xolani Sabelo.
In this study, two plant species, Schefflera umbellifera (Araliaceae) and
The influence of surfactants on the solubility of acenaphthene and phenanthrene and their extraction from spiked soils.
(2005) Ragoonandan, Sudika.; Jaganyi, Deogratius.
In the first phase of the study, the effect of five Safol surfactants on the aqueous solubility of phenanthrene and acenaphthene was determined. The fixed variables were temperature and ionic strength, while surfactant concentration and pH were varied. Quantification of the polyaromatic hydrocarbons (PAHs) was conducted by UV-Visible spectrophotometry. The surfactants had little or no effect on analyte solubilisation below the critical micelle concentration (CMC) while a linear relationship between surfactant concentration and amount of solubilised phenanthrene was observed above CMC concentrations. Safol 45E5 had the highest phenanthrene molar solubilisation ratio (0.83) of the five surfactants tested. The solubilisation of phenanthrene increased marginally (4.1 % for Safol 45E12 and 15.2 % for Safol 45E7) by decreasing the pH from 8 to 5. The concentration of solubilised acenaphthene was 8.4 % higher than phenanthrene in a 1 mM solution of Safol 45E7. The aqueous solubility of phenanthrene was enhanced 11.0, 21.2, 19.6, 15.9 and 14.7 times in 1 mM solutions of Safol 45E3, 45E5, 45E7, 45E9 and 45E12 respectively. Seasand, Longlands sand, Longlands soil and a standard soil sample were spiked with the two PAHs and aged for two weeks. API sludge provided by Sasol and unspiked samples of the above mentioned sorbents were subjected to determinations of organic matter content, particle size distribution and moisture content. The spiked soils and sands and the sludge samples were then washed in various concentrations of Safol 45E7 (0.5, 1.0 and 2.0 mM) at the same temperature used in the solubility studies. A soil mass to solution volume of lg to 10 mL was used. Analyses of the soil and sand samples were conducted by High Pressure Liquid Chromatography (HPLC). Using a 2 mM Safol 45E7 surfactant solution, 100 % and 90 % of phenanthrene and acenaphthene were respectively extracted from Longlands sand and 88 % and 100 % of phenanthrene and acenaphthene were removed from seasand. 8.4 % phenanthrene and 8.17 % of acenaphthene was removed from Longlands soil, while 7.03 % phenanthrene and 6.64 % acenaphthene was removed from the standard soil sample. In the sand desorption studies, the amount of desorbed contaminants initially increased rapidly with increasing surfactant concentration, before levelling off at equilibrium. The amount of desorbed acenaphthene and phenanthrene increased exponentially with increasing surfactant concentration while contaminant concentrations decreased with increasing time in the Longlands soil and standard soil desorption experiments. Dry API sludge samples were also subjected to soil washing studies. The washed samples were Soxhlet extracted and analysed by gas chromatography. The 0.5 mM and 1 mM Safol 45E7 washed sludge samples showed respective phenanthrene peak area percent reductions representing a 44 % and 47 % extraction of phenanthrene from the API sludge.

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