The class of polycyclic hydrocarbons including adamantane, pentacyclo [5.4.0.02 ,6. 03,I0.05,9]undecane (PCU) and trishomocubane have proven to be an exciting investigation for synthetic chemists. Many derivatives have been shown to possess excellent antiviral and antibacterial properties, as well as potent anti-Parkinson agents. Some improve the lipophilic nature of biologically active drugs, while others affect the three-dimensional structure of peptides once incorporated as amino acid analogues. This investigation focussed on deriving routes to improve yields of racemic 4-amino-(D3)trishomocubane- 4-carboxylic acid (tris-amino acid), the synthesis of enantiomerically pure tris-amino acid, the incorporation of tris-amino acid into a short peptide, as well as the simulation of the rearrangement of PCU to trishomocubane by using computational tools. Research into developing a more efficient hydrolysis of trishomocubane-hydantoin (trishydantoin) to yield racemic tris-amino acid, led to the development of two novel compounds: the mono-Boc [Novel Compound 1, (NC1)] and bis-Boc [Novel Compound 2, (NC2)] protected hydantoin. Base hydrolysis of NC2 quantitatively yielded the racemic tris-amino acid, which was a significant improvement on previously documented synthetic routes. The first attempt to produce enantiomerically pure tris-amino acid was through the synthesis of diastereomeric derivatives of tris-hydantoin, chromatographic separation of the diastereomers, followed by base hydrolysis of the hydantoin ring to produce enantiomerically pure tris-amino acid. This research led to the development of two novel N-protected tris-hydantoin derivatives (NC3 and NC4). Failure to chromatographically separate the diastereomers resulted in the abandonment of this particular route. The use of enzymes was, therefore, attempted to produce enantiomerically pure tris-amino acid. A novel ester derivative of tris-amino acid (NC5) was synthesised, which was followed by the application of Pig Liver Esterase (PLE). PLE is an enzyme which cleaves ester functionalities. Some success was achieved but the extremely low yields of enantiomerically pure tris-amino acid did not warrant this enzyme as a viable route for production of the desired product. Solid phase techniques were employed for the production of a tripeptide consisting of alanine-glycine-tris-amino acid (ala-gly-tris). Some difficulty was encountered in extending the amino acid sequence due to suspected Schiff base interaction between the free amino group of tris-amino acid and the carbonyl functionality of glycine in the second position. A computational study, using ab initio methods, was performed on the rearrangement of the PCU diol to 7-fluoro-11-hydroxy-trishomocubane. Two mechanisms (Proposed Mechanism 1 and Proposed Mechanism 2) were explored and both showed that the stereochemistry of the hydroxyl groups has only a marginal influence on the transition state energies of the various isomers. Both mechanisms were also indicated to occur through an intramolecular SN2 mechanism. / Thesis (M.Sc.)-University of Natal, Durban, 2003.

The study involves the investigation of the chemical composition of some marine organisms. This entails collecting the organism, extracting compounds from it and separation, characterization and identification of these compounds. Marine chemistry has been ignored by many scientists in the past and it is for this reason that these organisms have been investigated, with the aim of discovering their chemistry and also finding new compounds which might be of value in our society. Such value may be the medicinal benefit and/or the understanding of some toxicological effect of some species. This study was conducted on Codium extricatum, Palythoa natalensis, Zoanthus sansibaricus and Zoanthus durbanensis all of which were collected from reefs situated at the southern part of Durban in KwaZulu-Natal (KZN). Carpobrotus edulis was another organism that was used in this work. The plant normally occurs on sand dunes. This, however, was collected from the terrestrial environment within the premises of University of Natal (Durban). Sterols, i.e., compound l, 2 and compound 4 were obtained from both the Codium and Zoanthus genera. Zoanthus also gave compounds which are derivatives of genetic material and these include inosine nucleoside, adenine nucleoside and guanine nucleoside. Zoanthus further gave a compound which is aromatic in nature i.e., compound 5 and this belongs to a class of compounds known as the tyramines. Cinnamic acid was found from Carpobrotus edulis. The structures of all compounds were elucidated by conducting a number of experiments using spectroscopic methods. These included nuclear magnetic resonance spectroscopy (n.m.r), mass and infrared spectroscopy. / Thesis (M.Sc.)-University of Natal, Durban, 2000.

This work is an account of investigations into the chemistry of one of the members of the Amaryllidacae family, Ammocharis coranica, and one of the members of the Fabaceae family, Sophora velutina. Chapter one is an account of the extractives from the bulbs of Ammocharis coranica. In all, twelve compounds, eight alkaloids and four cycloartane compounds have been isolated of which one alkaloid and one cycloartane compound have not been described previously. Plants belonging to the Amaryllidacae family have been used by traditional healers, especially in Africa, to treat a range of illnesses and diseases. The alkaloids isolated from these plants have been shown to exhibit responses to muscle stimulant, antiviral, antifungal, antiyeast, antimalarial, cytotoxic and antitumoural activities. Ammocharis coranica is used by the Zulu tribe in South Africa to treat any illness believed to be caused by witchcraft. Alkaloids from the three most common types among the isoquinoline group were found in this species. These are lycorine, 1-O-acetyllycorine, hippadine, acetylcaranine, and the novel 1-O- acetyl-9-norpluviine from the lycorine type, 6-α-hydroxypowelline from the crinine type and hamayne and crinamine from the haemanthamine type. Cycloartane compounds have not been reported previously from the Amaryllidaceae family. All four cycloartane compounds had a common side chain, containing an olefinic methylene group at position 24, but differed in their substituents at positions 3 and 4. These compounds were found to be 24-methylenecycloartan-3β-ol, cycloeucalenol, cycloeucalenone and the novel compound 4-methylenepollinastanone. Chapter two is an account of the extractives from the seeds of Sophora velutina. The seeds of other Sophora species have been used in traditional ceremonies by the Indians of the Southwest United States and adjacent Mexico because of their hallucinogenic activity. The seeds of Sophora velutina subsp. zimbabweensis found in Zimbabwe are suspected to have historically been used by the natives for their hallucinogenic properties. These plants have been known to contain several quinolizidine alkaloids, flavonoids and isoflavonoids. One alkaloid, N-methylcytisine and two isoflavones, pseudobaptigenin and calycosin, as well as the common phytosterol, β-sitosterol were isolated from the seeds of this species. N-methylcytisine is a common quinolizidine alkaloid, isolated previously from several Sophora species and pseudobaptigenin and calycosin are well known isoflavones, isolated previously from several species in the Fabaceae. / Thesis (M.Sc.)-University of Natal, Durban, 1999.

This thesis describes a phytochemical investigation of four medicinal plants, namely, Agave attenuata (Agavaceae), Balanites maughamii (Balanitaceae), Astrotrichilia parvifolia (Meliaceae) and Combretum fragrans (Combretaceae). Investigations of A. attenuata and B. maughamii were undertaken as biological studies have shown that these plants possess anti-bilharzial properties. Schistosomiasis is an important public health issue in South Africa and attempts to deal with infected rural communities have forced scientists to focus their attention on snail control using plant molluscicides. A. attenuata yielded two glycosides, timosaponin A III (compound I) and 5?-pregn-16-en-20one- 3?-O-tetrasaccharide (compound II), while a coumarin, scopoletin (compound III) and a sterol, stigmasterol (compound IV) were isolated from B. maughamii A dammarane, shoreic acid (compound V) was isolated from A. parvifolia, this formed part of an ongoing investigation into the Meliaceae of Madagascar. Plants of the family Combretaceae are widespread in Africa and are used by traditional healers for a wide range of illnesses. The leaves and bark are used abundantly, however, the winged fruits are never eaten as they are highly toxic to animals and humans. The leaf surface is covered with epidermal scale-like trichomes through which acidic triterpenoid mixtures are secreted. Six lupane-type triterpenoids were isolated from C. jragrans, namely, lupeol (compound VI), lupenone (compound VII), lupeol 3?- docosanoate (compound VIII), lupeol 3?-eicosanoate (compound IX) hennadiol (compound X) and 30hydroxylupenone (compound XI). All the above compounds were isolated by column chromatography and the structures were elucidated by means of NMR spectroscopy, mass spectrometry and infra red spectroscopy. / Thesis (M.Sc.)-University of Natal, Durban, 2000.

As cyanobacteria (also known as blue green algae) produce a range of cyclic peptides which are highly toxic, capillary electrophoresis and associated techniques have been investigated to assess their applicability for toxin monitoring in the water bodies of kwaZulu Natal, South Africa. Capillary electrophoresis (CE) is a technique in which charged molecules can be efficiently separated in a buffer solution within a capillary tube under the influence of a strong electric field. Two CE modes, namely capillary zone electrophoresis (CZE) and micellar electrokinetic capillary chromatography (MECC) were initially evaluated using a laboratory-built CE instrument. The former mode lacked selectivity due to the similar charge to size ratio of the algal toxins. However, with the latter mode, incorporation of a surfactant (sodium dodecyl sulphate) into the buffer, produced sufficient resolution between components. Parameters including surfactant concentration, buffer ionic strength, buffer pH and operating voltage were systematically optimized to separate the four algal toxins under investigation (microcystin YR, microcystin LR, microcystin RR and nodularin). The optimum separation conditions were: 30 mM borax, 9 mM sodium dodecyl sulphate, pH 9.18, 30 kV applied voltage, 10 s hydrodynamic injection, 70 cm x 50 Ilm Ld. bare fused silica capillary (LEFF 40 cm) and UV detection at 238 nm. Under these conditions, typical detection limits were in the low ng/IlL range (14.13 ng/IlL for microcystin LR to 29.85 ng/ILL for nodularin). The MECC method was evaluated in terms of migration time precision, efficiency and resolution, peak area and normalised peak area precision. Standard deviation values for retention times acquired using replicate electrokinetic injections ranged from 0.018 to 0.054 and 0.069 to 0.148 for hydrodynamic injections. Normalised peak area precision for replicate hydrodynamic injections were in the range 84 to 97 % RSD, while improved % RSD values of 11.5 to 18.7 were achieved for electrokinetic injections. Due to poor precision resulting from the lack of automation on the laboratory built CE system, poor correlation between increasing concentration and a corresponding change in normalised peak areas were achieved. The MECC method developed was applied to the analysis of an algal scum extract to illustrate the technique. A general problem with CE is that it suffers from poor detection sensitivity. Hence in this study, alternative injection modes, sample concentration strategies and alternative detection techniques were investigated in an attempt to improve detection limits for algal toxins. Using optimized electrokinetic injection conditions, detection limits were five to ten times better than those obtained with hydrodynamic injections. On-line sample concentration methods were partially successful. Field amplified back and forth MECC in which analyte injected in the entire column volume and subsequently focused in a narrow band by manipulating the electric field, resulted in an enormous sensitivity enhancement that ranged from 197 times for microcystin RR to 777 times for microcystin YR when compared to hydrodynamic injections. Field amplified sample stacking (FASI) was ineffective for toxin preconcentration, while electro-extraction produced detection limits ranging from 0.27 ng/J.tL for microcystin YR to 1.08 ng/J.tL for microcystin RR. Solid phase extraction, in which analytes are first trapped and concentrated on HPLC material in a cartridge and then eluted in a more concentrated form for injection, was found to be practical only in the offline mode. A concentration detection limit of less than 0.002 ng/J.tL was obtained. Attempts with on-line solid phase extraction failed due to problems associated with coupling the cartridge with the separation capillary. Finally, laser induced fluorescence (LIF) detection was investigated as an alternative to UV detection. Unfortunately, the algal toxins were not amenable to LIF detection because tagging with the fluorescent moiety, fluorescein isothiocyanate (FITC), was prevented by the stereochemistry of these cyclic peptides. A comparative study between HPLC and MECC revealed that the former displayed poor efficiency peaks and long analysis times for toxin analysis. However HPLC was superior in terms of retention time precision (0.12 to 0.64 % RSD) and area precision (1.78 to 2.86 % RSD). Mass detection limits for MECC (0.0142 to 0.0603 ng) were far superior to those achieved by HPLC (0.55 to 1.025 ng). In addition to HPLC and MECC, a preliminary investigation of micro-high performance liquid chromatography (J.tHPLC) and capillary electrochromatography (CEC) for the analysis of algal toxins was made using 50 J.tm Ld. capillary columns packed in-house, with reverse phase HPLC packing material. / Thesis (M.Sc.)-University of Natal, 1997.

The concentrated protein fractions of soyabeans, known as soya protein isolate, was produced by three different methods from the same raw material namely defatted soya flakes. Extraction of the soluble fraction of the raw material is common to all three methods. A study was therefore undertaken to optimise the extraction process conditions in terms of time, temperature, pH, extraction time, extraction volume and raw material particle size, thereby maximising yields of soluble material. The three different methods, namely isoelectric precipitation, ultrafiltration and swollen gel technology were then used to separate the soluble and non-soluble protein fractions. Both the isoelectric and ultrafiltration methods gave good yields of finished product, with the ultrafiltration process giving the better overall yield, but the swollen gel method gave disappointing results and was not feasible in practice. Functional properties of the products from the isoelectric and ultrafiltration methods were compared and found to be broadly similar although different in certain respects from those of commercial soya isolates. Levels of the anti-nutritional factors trypsin inhibitor and phytate in products from the three processes were determined and the substantial differences observed in trypsin inhibitor levels were further investigated. Determination of lysinoalanine levels was also attempted but the results obtained were unsatisfactory. Amino acid composition and polyacrylamide gel electrophoresis were used to compare the chemical composition of products from the three processes. The comparative economics of the isoelectric and ultrafiltration processes for large scale production of soya protein isolates were evaluated, taking into account the comparative efficiencies of the two processes as determined during the study. It was established that, while the isoelectric process initially appears more economical, it may be possible to modify the ultrafiltration process in such a manner as to make it more economical than the isoelectric process. Overall figures however indicate that the manufacture of soya protein isolate in South Africa is not currently a viable economic proposition, due to high raw material costs. / Thesis (M.Sc.)-University of Natal, 1995.

Momordica foetida Schum. & Sond. (Cucurbitaceae), locally known as iNtshungu, is widely used by the Zulu people of Natal-KwaZulu for the treatment of a variety of ailments. The dried leaves leaves and stems of this plant was subjected to soxhlet extraction by refluxing with hexane, chloroform and methanol successively. Thin layer chromatography of the chloroform extract of the leaves revealed a multiplicity of compounds. The chloroform extract was further partitioned with sodium hydroxide resulting in an organic and aqueous phase. The organic phase, containing extract A, afforded two compounds, viz. compounds 1 and 2. The basic aqueous fraction was neutralised and re-extracted with chloroform to give extract B, affording five compounds, viz. compounds 3,4,5,6 and 7. Structural elucidation was accomplished by techniques such as IH and 13C NMR spectroscopy, HETCOR, COSY, FTIR and High Resolution Mass Spectrometry. Compounds 1 and 2 were identified as cucurbitane triterpenoids known as momordicines which had been previously discovered in the related species of this plant, Momordica charantia L. The remaining five compounds were identified as novel compounds, although natural derivatives of compounds 6 and 7 had been isolated previously from Momordica charantia L. Compounds 3-7 were each isolated as an epimeric mixture but it was possible to select the resonances corresponding to the major epimer. These five epimers were respectively identified as 5, 19-epoxy-19(R)-hydroxy-25-methoxy-5β- cucurbita-6,23-diene-3β-ol [102], 5,19-epoxy-19(R),25-dihydroxy-5β-cucurbita- 6,23-diene-3β-ol [103], 5,19-epoxy-19(R)-methoxy-25-hydroxy-5β-cucrbita- 6,23-diene-3β-ol [104], 5,19-epoxy-25-methoxy-5β-cucurbita-6,23diene- 3β-ol [105] and 5,19-epoxy-19(R),25-dimethoxy-5β-cucurbita-6,23diene- 3β-ol [106]. Appropriate reactions were performed, where possible, on the compounds isolated in order to confirm their identity. / Thesis (M.Sc.)-University of Natal, Durban, 1994.

SAPPI SAJCCOR, whose factory is situated south of Durban, South Africa, is one of the few paper and pulp mills that uses the acid sulphite process with calcium and magnesium bases to produce a high-grade cellulose pulp. Four streams of effluent, namely, the calcium - spent liquor stream, the magnesium condensate stream and two streams from the bleaching effluent are produced during this sulphite pulping process and they contain a variety of organic compounds extracted from the wood. Characterisation of the effluent was based on isolation using column chromatography and identification using NMR techniques. A range of constituents, such as lignans and lignin - type precursors, a trilerpenoid and fatty acids were isolated and identified. X-ray diffraction was used to identify an inorganic residue obtained from the calcium - spent liquor stream and gas chromatography/mass spectrometry was used to identify a wax residue. which builds up in the process. In addition to this, the carbohydrate content of the four streams of effluent was detennined using UV/visiblc spectroscopy. / Thesis (M.Sc.)-University of Natal, Durban, 2001.

The work described in this thesis concerns the synthesis and study of the coordination behaviour of the 6-anilino-2,2'-bipyridyl (Habipy), 6-N-methylanilino-2,2'-bipyridyl (mabipy), 6-piperidyl2,2'.- bipyridyl (pipbipy) and 2,2'-bipyridin-6-one (Hobipy) ligands. Chapter one reviews the coordination chemistry of the 2-aminopyridyl (Rap), 2-hydroxypyridyl (Hhp) and the 2-(2-pyridyl)-I,8-naphthyridine (pynp) ligands. These ligands are closely related to Habipy, mabipy, pipbipy and Hobipy in that they share a common NCN or NCO fragment. Thus the review of their coordination behaviour provides insight into the expected coordination of the Habipy, mabipy, pipbipy and Hobipy ligands. The synthesis and characteristaion of the novel Habipy, mabipy and pipbipy ligands are reported in Chapter two. X-ray crystal structure determinations of mabipy and pipbipy reveal that the geometry about the exocyclic nitrogen atom in both ligands is nearly planer, suggesting substantial overlap of the nitrogen lone pair orbital with the 1t electron system of the bipyridyl rings. In both mabipy and pipbipy the N3-C 10 bond lengths are shorter then normal N-C single bonds. In Chapter three -the synthesis and characterisation of copper(I) complexes containing mabipy, pipbipy and Habipy, and a copper(II) complex containing mabipy are reported. The copper(I) complexes have the general formula [Cu(l12-L)2r, where L= mabipy 1, pipbipy 2 or Habipy 3. The structures of complexes 1 and 2 are determined by X-ray crystallography. In complexes 1- 3 the bipyridyl fragments of mabipy, pipbipy and Habipy chelate while the exocyclic nitrogen atoms remain free. The crystal structures of 1 and 2 reveal that the exocyclic nitrogens have a planar geometry as was the case in the uncoordinated ligand. The crystal structure of [Cu(1l2-mabipY)2f+ (4) is determined by X-ray crystallography and is very similar to that of the copper(I) species. Coordination of the mabipy ligand in 4 is the same as that in 1 and the exocyclic nitrogen in 4 is also planar. The redox couple 4/1 is shown to be electrochemically reversible with EV2= 0.45 V. In Chapter four the synthesis and chararcterisation of dinuclear complexes containing the Ru2 2+, Ru/+, Mo24+and ~4+ cores are reported in which the abipy ligand bridges two metal centres. The complexes [Rulll-L)lCO)4], where L= abipy 5 or obipy 6, were synthesised by the r~action of the free ligands with [{RuiCO)102CCH3)2}n] in toluene. The structures of5 and 6 are determined by X-ray crystallography and show the ligands bridging the Ru(I) atoms in a head to tail fashion and occupy mutually cis positions about the octahedral Ru(I) atoms. The Ru-Ru separations in 5 and 6 are 2.668(1) and 2.671(1) A respectively. The reaction of Habipy with [Rui02CCH3)4CI]n was found to afford the mixed valence species [Ruill-abipy)(02CCH3)3CI] (7), the structure of which is determined by X-ray diffraction methods. The structure of7 reveals one abipy ligand bridging the two ruthenium atoms as in 5. The Ru-Ru separation in 7 is 2.294(2) A. The reaction of [Moi02CCH3)4] with habipy in methanol affords (Moill-abipy)(02CCH3)3] (8). The structure of 8 is determined by X-ray diffraction methods and reveals one abipy ligand bridging two quadruply bonded molybdenum atoms which have a Mo-Mo separation of 2.094(2) A. The [Rhlll~abipy)(02CCH3)iH20)] (9) is formed from the reaction of [Rh i02CCH3)4] with Habipy in methanol. The structure of [Rh2(Il-abipy)(02CCH3)iNCPh)] is determined by X-ray diffraction methods and shows the abipy ligand bridging two Rh(II) atoms which are separated by 2.399(1) A. This chapter is concluded with a discussion of the possiblity of substitution of more than one acetate ligand by the abipy ligand in terms of 'hard' and' soft' acid-base theory and synthetic methods. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 1996.

In this study two medicinal plant species, namely Artemisia afra Jacq. ex. Willd and Elytropappus rhinocerotis Less. (L.f) (= Dicerotamnus rhinocerotis Koekemoer), both belonging to the family Asteraceae, have been investigated and different compounds isolated and characterised. Both species are important plants used in traditional medicine in general in Africa and particularly in South Africa. A. afra, commonly called "African wormwood" is one of 400 species belonging to the genus Artemisia and it is the only one indigenous to Africa. E. rhinocerotis is one of eight Elytropappus species which are all restricted to the Cape floristic region. The aim of this study was to investigate the phytochemistry of these species. In total fifteen compounds were isolated and characterised. From the E. rhinocerotis extract, four known compounds, labdanolic acid, methyl labdanolate, 6, 7- dimethoxycoumarin and a sesquiterpene viridiflorol were isolated. These compounds were not previously reported from E. rhinocerotis. Two different chemotypes of A. afra were studied and eleven compounds were isolated. These compounds include sesquiterpenes such as taurin, artesin, maritimin, artemin, norsantolinifolide, santolinifolide A, and reynosin, a flavonoid, 5- hydroxy-7,4-dimethoxyflavone, a coumarin called scopoletin or 7-hydroxy-6- methoxycoumarin and other aromatic compounds such as p-hydroxyacetophenone, and 2,4-dihydroxy-6-methoxyacetophenone. Except for taurin, scopoletin and 5-hydroxy-7, 4- dimethoxyflavone , none of these other compounds has been reported previously from A. afra. This study has shown that A. afra contains a large number of sesquiterpenoids, mostly from the eudesmane-type. Structural elucidation of different compounds was performed using mainly NMR spectroscopy. Other methods used for identification include LC-MS and infrared spectroscopy. The major compound, labdanolic acid, is known to selectively inhibit cyclooxygenase-2, an enzyme associated with inflammation. The presence of labdanolic acid in the plant may account for its traditional use as an anti-inflammatory. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2009.