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Photodynamic antimicrobial chemotherapy activities of porphyrin- and phthalocyanine-platinum nanoparticle conjugates

- Managa, Muthumuni Elizabeth

Authors: Managa, Muthumuni Elizabeth
Date: 2015
Subjects: Photochemotherapy , Anti-infective agents , Porphyrins , Phthalocyanines , Platinum , Nanoparticles , Bioconjugates , Electrospinning
Language: English
Type: Thesis , Masters , MSc
Identifier: vital:4539 , http://hdl.handle.net/10962/d1017919
Description: This work reports on the conjugation of differently shaped Pt nanoparticles (PtNPs) with ClGa(III) 5,10,15,20-tetrakis-(4-carboxyphenyl) porphyrin (1) as well as chloro - (5,10,15,20-tetrakis (4- (4- carboxy phenycarbonoimidoyl) phenyl) porphyrinato) gallium(III) (2) The work also reports on platination of dihydroxosilicon octacarboxyphthalocyanine (OH)₂SiOCPc (3) to give dihydroxosilicontris(diaquaplatinum)octacarboxyphthalocyanine (OH)₂SiOCPc(Pt)₃ (4). The resulting conjugates were used for photodynamic antimicrobial chemotherapy against S. aureus, E. coli and C. albicans. The degree of photo-inactivation is dependent on concentration of the conjugates, light dose (fluence) and illumination time. The log reduction obtained for 1 when conjugated to cubic PtNPs was 4.64 log (which indicate 99.99 percent of the bacteria have been killed), which is much higher than 3.94 log unit for 1-hexagonal PtNPs and 3.31 log units for 1-unshaped PtNPs. Complex 2 conjugated to hexagonal PtNPs showed 18 nm red shift in the Soret band when compared to 2 alone. Complex 2 and 2-hexagonal PtNPs as well showed promising photodynamic antimicrobial chemotherapy (PACT) activity against S. aureus, E. coli and C. albicans in solution where the log reduction obtained was 4.92, 3.76, and 3.95 respectively for 2-hexagonal PtNPs. The singlet oxygen quantum yields obtained were higher at 0.56 for 2-hexagonl PtNPs in DMF while that of 2 was 0.52 in the same solvent. This resulted in improved PACT activity for 2-hexagonal PtNPs compared to 2. Complex 4 showed slight blue shifting of the absorption spectrum when compared to complex 3 The antimicrobial activity of 4 were promising as the highest log reduction value was observed when compared to the porphyrin conjugates.
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Date Issued: 2015

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Synthesis and characterization of NaYGdF4 upconversion nanoparticles and an investigation of their effects on the spectroscopic properties of two phthalocyanine dyes

- Taylor, Jessica Mary

Authors: Taylor, Jessica Mary
Date: 2014
Language: English
Type: text , Thesis , Masters , MSc
Identifier: http://hdl.handle.net/10962/54621 , vital:26594
Description: Sphere and star shaped NaYGdF4:Yb/Er(Tm) upconversion nanoparticles were successfully synthesized utilizing a methanol assisted thermal decomposition approach and their chemical, spectroscopic and fluorescence properties were fully characterized. In addition, their influence on the spectroscopic and fluorescence properties of two phthalocyanines (Pcs) (unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) and aluminium octacarboxy phthalocyanine (Cl)AlOCPc) was investigated. Upconversion nanoparticles were found to produce characteristic upconversion fluorescence emissions in the blue, green, red and NIR regions and were also shown to possess paramagnetic properties. Simple mixing with an H2Pc in toluene was found to exert no change on the spectroscopic or fluorescence properties of the Pc while covalent conjugation to a (Cl)AlOCPc resulted in a large Q band blue shift accompanied by a decrease in fluorescence lifetimes in DMSO. The red light excitation mediated singlet oxygen generation of the H2Pc mixed with upconversion nanoparticles was investigated and singlet oxygen fluorescence lifetimes were found to decrease in the presence of the nanoparticles. Upconversion mediated singlet oxygen generation, by way of resonance energy transfer to the Pc, was also attempted using 972 nm excitation; however, no singlet oxygen was detected utilizing singlet oxygen NIR emission detection. Pending further work using alternative singlet oxygen detection methods, this suggests that while upconversion nanoparticles possess excellent fluorescent imaging capabilities, they are relatively inefficient in inducing singlet oxygen production simply when mixed with phthalocyanines. Despite this, by combining phthalocyanines and upconversion nanoparticles, we present a system capable of: multimodal imaging, using both upconversion and phthalocyanines emissions, singlet oxygen generation, via direct excitation of the phthalocyanine with red laser light, and, possibly, magnetic resonance imaging, as a result of doping the upconversion nanoparticles with Gd3+ ions.
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Date Issued: 2014

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Photosensitizer, pH sensing and optical limiting properties of BODIPY dyes

- May, Aviwe Khanya

Authors: May, Aviwe Khanya
Date: 2018
Subjects: Dyes and dyeing -- Chemistry , Halogenation , Photochemotherapy , Bromination , Photosensitizing compounds , Nonlinear optics , BODIPY dyes
Language: English
Type: text , Thesis , Masters , MA
Identifier: http://hdl.handle.net/10962/63964 , vital:28515
Description: A series of BODIPY dyes have been successfully synthesised and structurally characterised to examine the effect of halogenation at the 2,6-positions and the introduction of styryl and vinylene groups at the 3,5-positions. The photophysical properties were studied, to assess the effect of the enhancement of the rate of intersystem crossing through halogenation on the fluorescence properties and the generation of reactive oxygen species. This is important in the assessment of the suitability of applying these molecules as photosensitizer dyes for photodynamic therapy and photodynamic antimicrobial chemotherapy. Upon bromination, the dyes showed moderately high singlet oxygen quantum yields. The inclusion of BODIPY dyes into cyclodextrins was explored since it makes them water soluble and hence suitable for biomedical applications, but no singlet oxygen was detected in aqueous media for the inclusion complexes. In order to red-shift the main spectral band of the BODIPY dyes into the therapeutic window, styryl groups were introduced at the 3,5-positions via a modified Knoevenagel condensation reaction. Since the main spectral band lies well above 532 nm, the second harmonic of the Nd:YAG laser, there is relatively weak absorbance at this wavelength. The 3,5-distyryl and 3,5-divinylene BODIPY dyes were assessed for their potential utility for application in nonlinear optics (NLO), and they demonstrated typical nonlinear absorption behaviour characterised by reverse saturable absorption (RSA) in z-scan measurements. Furthermore, the dyes possess excellent optical limiting parameters, such as their third-order suspectibility and hyperpolarizability values, in a wide range of solvents. One dye containing dimethylamino moieties on styryl groups attached at the 3,5-positions was assessed for potential application as an on/off fluorescence sensor. The dye proved to be successful, since intramolecular charge transfer in the S1 state was eliminated in the presence of acid and this results in a fluorescence “turn on” effect. This process was found to be reversible with the addition of a base.
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Date Issued: 2018

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A study of petrol and diesel fuel blends with special reference to their thermodynamic properties and phase equilibria

- Heyward, Caroline

Authors: Heyward, Caroline
Date: 1986
Language: English
Type: Thesis , Masters , MSc
Identifier: vital:21167 , http://hdl.handle.net/10962/6695
Description: The ternary phase behaviour of the n-heptane-l-propanol-water system was studied and compared with the theoretical prediction based on the UNIQUAC model for non-electrolyte solutions. The results showed that this model adequately approximated experimental studies. The excess enthalpies and excess volumes for several binary mixtures were determined. The excess enthalpies were measured using a LKB flow microcalorimeter and the excess -volumes determined using a PAAR densitometer. The study showed that no significant enthalpy or volume changes occurred when petrol/n-heptane were mixed with alcohols. Ternary phase diagrams, including tie lines have been determined for a number of petrol-alcohol-water systems (including the Sasol blend of alcohols). The tie line results show that the concentration of water in the water-rich layer is strongly dependent on the type of alcohol used. The Sasol alcohol blended with petrol resulted in a high water concentration in the water-rich layer which forms on phase separation. This is believed to contribute significantly to the corrosion problems experienced by motorists using the Sasol blended fuel on the Witwatersrand. The effect of temperature on several of these blends was included in the study. Diesel-alcohol blends and the co-solvent properties of ethyl acetate investigated. Ethyl acetate ensures miscibility at low concentrations for diesel-ethanol blends. Octyl nitrate and two cetane improvers from AECI were assessed in terms of their ability to restore cetane rating of blended diesel fuel to that of pure diesel fuel. The results indicated that all three samples were successful in this application.
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Date Issued: 1986

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Synthesis, characterisation and electrocatalytic behaviour of three series of Metal Organic Frameworks

- Murinzi, Tafadzwa Wendy

Authors: Murinzi, Tafadzwa Wendy
Date: 2020
Subjects: Electrochemistry , Metal-organic frameworks , Polyoxometalates , Fourier transform infrared spectroscopy , Electrocatalysis , Cysteine
Language: English
Type: text , Thesis , Doctoral , PhD
Identifier: http://hdl.handle.net/10962/167598 , vital:41495
Description: Metal organic frameworks (MOFs) have received a lot of attention over the past few years due to their vast range of interesting properties and applications, such as catalysis, environmental sensing and storage. This wide range of potential applications is afforded by careful selection and manipulation of the components chosen in assembling of MOFs. In this study, three series of MOFs were synthesized from Co(II), Cu(II) and Mo(VI) polyoxometallates with either 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid or 2,6- pyridinedicarboxylic acid as the ligands. In series 1, the common 1,3,5- benzenetricarboxylic acid MOF, HKUST-1, and POM modified HKUST-1 compounds involving encapsulation and encorporation of the POM were utilised. In series 2, flexible cobalt(II) benzenepolycarboxylate MOFs which investigated the effect of varying the degree of carboxylate substituent were utilised. In series 3, flexibly reduced heterocyclic polycarboxylate MOFs using 2,6-pyridine dicarboxylate were utilised. Solvothermal and slow evaporation synthesis conditions were employed. Where single crystals of good quality were produced, single crystal X-ray diffraction (SC-XRD) was employed for structural elucidation. In the absence of such crystals, a combination of elemental analysis, inductively coupled plasma optical emission spectrometry (ICP-OES) and powder X-ray diffraction (PXRD) was used. Characterization of the MOFs was done by Fourier transform infrared spectrometry (FTIR) and thermal methods, namely thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The electrocatalytic potential of the compounds in the oxidation of L-cysteine was then investigated using a variety of techniques. Cyclic voltammetry was used for L-cysteine detection whilst chronoamperometry and differential pulse voltammetry were used to determine the nanoprobes’ sensitivity, rate constants and detection limits. Electrochemical impedence spectroscopy was used to investigate the charge transfer resistance (RCT) and electron transfer kinetics. Of the three, series 3 gave the best signals and sensitivities for electrocatalysis of L-cysteine followed by series 2 and lastly series 1. Series 2 showed the highest stability and series 1 required the least overpotential. The results highlight the effects of different metal centres and ligands on electrocatalysis. The application of MOFs in electrochemistry is a relatively new field making the findings of this study a significant addition to the body of knowledge.
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Date Issued: 2020

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Effect of substituents on the photophysical properties and nonlinear optical properties of asymmetrical zinc(II) phthalocyanine when conjugated to semiconductor quantum dots

- Mgidlana, Sithi

Authors: Mgidlana, Sithi
Date: 2019
Subjects: Nonlinear optics , Quantum dots , Phthalocyanines , Zinc
Language: English
Type: text , Thesis , Masters , MSc
Identifier: http://hdl.handle.net/10962/97152 , vital:31404
Description: Various characterization techniques have been used to characterize the synthesized asymmetrical zinc phthalocyanines (ZnPc) derivatives. Techniques include Ultraviolet-visible (UV-vis) spectrophotometry, matrix assisted laser desorption time of flight mass spectrometry (MALD-TOF MS), proton nuclear magnetic resonance (1H-NMR), elemental analysis and Fourier-transform infra-red spectroscopy (FT-IR). The complexes are covalently linked to core/shell and core/shell/shell semiconductor quantum dots (SQDs) via amide bond formation. Photophysical properties of complexes improved in the presence of semiconductor quantum dots (SQDs). SQDs contain cadmium/telluride (CdTe) as core, coated in the first shell with zinc selenide (ZnSe) or zinc sulfide (ZnS) and with zinc oxide (ZnO) in second shell. The photophysical properties of the phthalocyanine (Pc) complexes and their conjugates with SQDs are investigated in solution. Triplet quantum yields of complexes improved in the presence of semiconductor quantum dots. The optical limiting behaviour of the Pc complexes and conjugates are assessed using the open aperture Z–scan technique at laser excitation wavelength of 532 nm with 10 ns pulse. Pcs complexes showed good nonlinear optical response with higher nonlinear absorption coefficient. The conjugates afforded higher nonlinear absorption coefficient than Pc complexes alone.
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Date Issued: 2019

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A statistical study of the errors involved in the sampling and chemical analysis of soils and plants, with particular reference to citrus and pineapples

- Steyn, Willem Johannes Abraham

Authors: Steyn, Willem Johannes Abraham
Date: 1958
Subjects: Soil chemistry , Plants -- Analysis , Soils -- Analysis
Language: English
Type: Thesis , Doctoral , PhD
Identifier: vital:4506 , http://hdl.handle.net/10962/d1013291
Description: 1. Accurate and reproducible methods for the determination of N and acid- extractable P in soils are described. The variations in N, P, and K found by intensive sampling of three different soil types are presented. 3. Suggestions for the adequate sampling of soils for various purposes arc given. 4. A study is presented of the preparative stages in leaf analysis (washing, drying, grinding and storage) as applied to citrus and pineapple leaf material. Likely errors are pointed out and procedures whereby these may be minimised are described. 5. A reliable wet-ashing procedure for obtaining leaf solutions is described. 6. Accurate and reproducible methods for the determination of total N, P,. K, Ca, Mg, Na, Fe, Mn, Zn and Cu in citrus and pineapple leaves are presented. 7. It is shown that diurnal variations in nutrient concentrations occur in citrus and pineapple leaves. 8. The variations in N, P, K, Ca, Mg, Na, Fe, Mn, Zn and Cu, occurring from tree to tree in 3 different Navel orange blocks are presented. It is shown that if all these elements are to be represented . to within 10% of the mean values on a 19 : 1 probability level, all the trees in the blocks would have to be sampled. Reasonable sampling procedures for various purposes are suggested. 9. The variations in N, P, K, Ca, Mg, Fe, Mn, Zn and Cu, occurring in 3 different Cayenne pineapple plantations are presented and described. Suitable sampling procedures are suggested.
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Date Issued: 1958

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Synthetic and bioactivity studies of antiplasmodial and antibacterial marine natural products

- Young, Ryan Mark

Authors: Young, Ryan Mark
Date: 2012
Subjects: Antibacterial agents Marine natural products Marine pharmacology Plasmodium falciparum Staphylococcus aureus Isocyanides Imidazoles
Language: English
Type: Thesis , Doctoral , PhD
Identifier: vital:4378 , http://hdl.handle.net/10962/d1005043
Description: This thesis is divided into two parts, assessing marine and synthetic compounds active firstly against Plasmodium falciparum (Chapter 3 and 4) and secondly active against methicillin resistant Staphylococcus aureus (MRSA, Chapter 5). In Chapter 3 the synthesis of nine new tricyclic podocarpanes (3.203-3.207 and 3.209-3.212) from the diterpene (+)-manool is described. Initial SAR study of synthetic podocarpanes concluded that the most active compound was a C-13 phenyl substituted podocarpane (3.204, IC₅₀ 6.6 μM). By preparing analogues with varying halogenated substituents on the phenyl ring (3.209-3.212) the antiplasmodial activity was improved (IC₅₀ 1.4 μM), while simultaneously decreasing the haemolysis previously reported for this class of compounds. Inspired by the antiplasmodial activity of Wright and Wattanapiromsakul’s tricycle marine isonitriles (2.16-2.21 and 2.24-2.27) an unsuccessfully attempt was made to convert tertiary alcohol moieties to isonitrile functionalities in compounds 3.188, 3.204-3.207 and 3.209-3.212. Over a decade ago Wright et al. proposed a putative antiplasmodial mechanism of action for marine isonitriles (2.4, 2.9, 2.15, 2.19 and 2.35) and isothiocyanate (2.34) which involved interference in haem detoxification by P. falciparum thus inhibiting the growth of the parasite. In Chapter 4 we describe how we successfully managed to scale down Egan’s β-haematin inhibition assay for the analyses of small quantities of marine natural products as potential β-haematin inhibitors. Our modified assay revealed that the most active antiplasmodial marine isonitrile 2.9 (IC₅₀ 13 nM) showed total β-haematin inhibition while 2.15 (IC₅₀ 81 nM) and 2.19 (IC₅₀ 31 nM) showed partial inhibition at three equivalents relative to haem. Using contempary molecular modelling techniques the charge on the isonitrile functionality was more accurately describe and the modified charge data sets was used to explore docking of marine isonitriles to haem using AutoDock. In Chapter 5 we describe how a lead South African marine bisindole MRSA pyruvate kinase inhibitor (5.8) was discovered in collaboration with colleagues at the University of British Columbia (UBC) and how this discovery inspired us to design a synthetic route to the dibrominated bisindole, isobromotopsentin (5.20) in an attempt to increase the bioactivity displayed by 5.8. We devised a fast and high yielding synthetic route using microwave assited organic synthesis. We first tested this synthesis using simple aryl glyoxals (5.27-5.32) as precursors to synthesize biphenylimidazoles (5.21-5.26), which later allowed us to synthesize the ascidian natural product 5.111. This method was sucessfully extended to the synthesis of deoxytopsentin (5.33) from an N-Boc protected indole methyl ketone (5.89). We subsequently were able to effectively remove the carbamate protection via thermal decomposition by heating the protected bisindole imidazole (5.90) in a microwave reactor for 5 min under argon. The synthesis of 5.20 resulted in an inseparable mixture of monoprotected and totally deprotected topsentin products, and due to time constraints we were not able to optimise this synthesis. Nonetheless our synthesis of the marine natural product 5.33 which was faster and higher yielding than previously reported routes could be extended to the synthesis of other topsentin bisindoles (5.138-5.140). Work towards this goal continues in our laboratory.
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Date Issued: 2012

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The chemistry of the wattle tannins

- Roux, David Gerhardus

Authors: Roux, David Gerhardus
Date: 1953
Subjects: Tannin plants , Tannins , Wattles (Plants)
Language: English
Type: text , Thesis , Doctoral , PhD
Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
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Date Issued: 1953

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The effect of ultraviolet and gamma irradation on soluble calf-skin collagen

- Davidson, Raymond John

Authors: Davidson, Raymond John
Date: 1967
Subjects: Collagen -- Hide powder Irradiation Solids -- Effect of radiation on Gamma rays -- Dose-response relationship
Language: English
Type: Thesis , Doctoral , PhD
Identifier: vital:4290 , http://hdl.handle.net/10962/d1003718
Description: Initially the present study was confined to the effects of ultraviolet irradiation on acid-soluble collagen. Such a study was undertaken in order to demonstrate the critical role played by tyrosine and phenylalanine in the intermolecular interaction of the telopeptides protruding from the rigid parent collagen molecule. Since both tyrosine and phenylalanine are photosensitive, and because the collagen telopeptides are relatively rich in these aromatic amino acids, carefully controlled degradation studies involving telopeptide liberation could be made. It became increasingly apparent during the course of investigation, that a better understanding of the subunit composition of thermally denatured acid-soluble collagen was necessary if a satisfactory interpretation of the irradiation studies was to be made. A subsequent study of the subunit composition of thermally denatured acid-soluble collagen resulted in the isolation and characterisation of two major and two minor dimeric components as well as the α- and β - subunits. Three acidic telopeptides and three basic telopeptides were also isolated from acid-soluble collagen during the course of the present study. The presence of the dimeric components while related directly to the method of preparation, suggested that acid-soluble collagen was largely dimeric in nature. Such a conclusion suggested an intermolecular rather than an intraolecular relationship between neutral-salt-soluble and acid-soluble collagen. While it is currently accepted that an intramolecular relationship exists between neutral-salt-soluble and acid-soluble collagen, such a relationship does not satisfactorily explain the very different solubility characteristics displayed by these soluble collagen extracts. With this in mind, and using the study on the subunit composition of thermally denatured acid-soluble collagen as a basis for comparison, the intra and intermolecular relationship between neutral-salt-soluble and acid-soluble collagen was investigated using ultraviolet and gamma irradiation. The effects of ultraviolet and gamma irradiation on soluble collagen preparations proved very similar. Although collagen samples were irradiated in solution from an ultraviolet source; and under anhydrous conditions from a gamma source, much the same degradation mechanism resulted. The initial depolymerisation of dimeric material followed by peptide fission, yielding irradiation-resistant crystalline portions of the parent triple helix, took place in both instances. At the same time, both studies indicated no significant differences in the intra or intermolecular structures of the neutral-salt-soluble and acid-soluble preparations investigated. The dimer content of neutral-salt-soluble collagen preparations was, however, noted to be smaller. To current methods for the preparation of soluble collagens, it may be concluded that such preparations are peptideless to some degree. While the native tropocollagen monomer with its full complement of telopeptide side chains may actively undergo linear polymerisation resulting in fibre formation, the soluble collagen preparations referred to above may only aggregate in a rather random fashion.
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Date Issued: 1967

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Studies in marine quinone chemistry

- Sunassee, Suthananda Naidu

Authors: Sunassee, Suthananda Naidu
Date: 2011
Subjects: Quinone Marine natural products Marine invertebrates Marine pharmacology Cancer -- Treatment
Language: English
Type: Thesis , Doctoral , PhD
Identifier: vital:4355 , http://hdl.handle.net/10962/d1005020
Description: This thesis is divided into two parts and the rationale of the research conducted is based on the cytotoxicity of the prenylated quinones 1.24-1.29, isolated from the South African nudibranch Leminda millecra, against oesophageal cancer cells. The first part (Chapters 2 and 3) of the thesis initially documents the distribution of cytotoxic and antioxidant prenylated quinones and hydroquinones in the marine environment. We have been able to show, for the first time, that these compounds can be divided into eight structural classes closely related to their phyletic distribution. Secondly, we attempted to synthesize the two marine natural products 1.24 and 1.26 in an effort to contribute to an ongoing collaborative search with the Division of Medical Biochemistry at the University of Cape Town for new compounds with anti-oesophageal cancer activity. Accordingly, we followed the published synthetic procedure for 1.26 and, although we were unable to reproduce the reported results, we have generated five new prenylated quinone analogues 3.53-3.55, 3.63 and 3.71, which are a potentially viable addition to our ongoing structure-activity relationship (SAR) studies. Moreover, we embarked on a 7Li NMR mechanistic study for the synthesis of 3.2 from 3.1 which rewarded us with an improved and reproducible methodology for this crucial reaction that is detailed in Chapter 3. The second part of this thesis (Chapters 4 and 5) is concerned with a synthetic, structural, electrochemical and biological exploration of the 1,4-naphthoquinone nucleus as a primary pharmacophore in our search for new chemical entities which can induce apoptosis in oesophageal cancer cells, thus contributing to our overall ongoing SAR study in this class of compounds. Seven new naphthoquinone derivatves (4.19, 4.30, 4.31, 4.33 and 4.46-4.48) of the natural products 2-deoxylapachol (2.44), lapachol (4.1) and β-lapachone (5.2) were synthesized and 2-(1`-hydroxy-`-phenylmethyl)-1,4-naphthoquinone (4.29) was found to be the most cytotoxic (IC50 1.5 μM) against the oesophageal cancer cell line WHCO1, while 5.2, which is currently in phase II clinical trials as an anticancer drug, was found to be similarly active (IC50 1.6 μM). Electrochemical investigations of the redox properties of the benzylic alcohol derivatives 4.29-4.31 indicated a higher reduction potential compared to their oxidized counterparts 4.45-4.48, and this finding has been correlated to the increased activity of 4.29-4.31 against the WHCO1 cell line. Additionally, 4.29 is synthetically more accessible than either 1.26 or 5.2 and potentially a lead compound in our search for new and more effective chemotherapeutic agents against oesophageal cancer
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Date Issued: 2011

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Some aspects of the chemistry of zirconium compounds relating to their combination with collagen

- Williams-Wynn, David Ernest Arthur

Authors: Williams-Wynn, David Ernest Arthur
Date: 1960
Subjects: Zirconium compounds , Collagen
Language: English
Type: Thesis , Masters , MSc
Identifier: vital:4513 , http://hdl.handle.net/10962/d1013456
Description: [Summary] Some properties of zirconium compounds in aqueous solution have been determined using physico-chemical techniques. Zirconium oxychloride was used as the source of zirconium in all detailed investigations; zirconium sulphate was used in a few cases for comparative purposes. The Stokes diaphragm cell method has been used to determine the diffusion coefficient of zirconium in hydrochloric acid solution. It was found that the diffusion coefficient fell progressively with time, a limiting value being reached 4 to 5 weeks after dissolving the salt, and it was demonstrated that particles in the aged solutions were more homogeneous than in freshly prepared solutions. The limiting values were concentration dependent; dilute solutions had a lower diffusion coefficient than the more concentrated solutions when measured at the natural pH. In the presence of added acid the rate of diffusion was increased until a limiting value was reached in 0.5 M acid. The addition of alkali or complexing acids reduced the rate of diffusion.
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Date Issued: 1960

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Investigation leading to a process for the synthesis of hydrogen sulphide from sulphur and certain lubricating oils derived from petroleum

- Schauder, H

Authors: Schauder, H
Date: 1952
Subjects: Hydrogen sulfide
Language: English
Type: Thesis , Masters , MSc
Identifier: vital:4499 , http://hdl.handle.net/10962/d1013160
Description: The primary object of the present study was to provide a process adaptable to prevailing South African conditions, for the manufacture of hydrogen sulphide. Such a process would also be suitable for use in other countries where the gas is not obtainable naturally or from refinery operations or as a by-product from other industries. Early in the study it was found that the literature embodying prior work was very scattered in character and had to be sought in many different fields of research. It was therefore decided to make the record of prior work as comprehensive as possible so as to provide, at the same time, a starting point tor future workers on related subjects. Intro., p. 1.
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Date Issued: 1952

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Studies towards the synthesis of novel tridentate ligands for use in ruthenium metathesis catalysts

- Millward, Tanya

Authors: Millward, Tanya
Date: 2009
Subjects: Ligands , Catalysis , Metathesis (Chemistry) , Ruthenium , Complex compounds
Language: English
Type: Thesis , Masters , MSc
Identifier: vital:4360 , http://hdl.handle.net/10962/d1005025 , Ligands , Catalysis , Metathesis (Chemistry) , Ruthenium , Complex compounds
Description: This work has focussed on the preparation of a variety of tridentate ligands, designed to form ruthenium complexes as potential metathesis catalysts. Various approaches to the tridentate, malonate-tethered imidazolidine system have been investigated, and a promising route to accessing ligands of this type is discussed. A tridentate malonate-tethered pyridine ligand has been successfully prepared and its dithallium salt has been accessed by hydrolysis with thallium carbonate; approaches to a longer-chain analogue have also been investigated. A thallium pyridine-2,6- dicarboxylate ligand has been has been successfully prepared, as have a range of pyridine diamine ligands, with various alkyl and aromatic substituents on the amine donor atoms. Preliminary investigations into the potential of these compounds as ligands for alkylidene ruthenium complexes are reported using molecular modelling techniques. The geometries and steric energies of the ligands and their corresponding complexes have been analysed, and results obtained from two different software packages are compared. Finally, some preliminary complexation studies have been undertaken.
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Date Issued: 2009

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Synthesis of zinc phthalocyanine derivatives for possible use in photodynamic therapy

- Matlaba, Pulane Maseleka

Authors: Matlaba, Pulane Maseleka
Date: 2003
Subjects: Photochemotherapy , Electrochemistry , Phthalocyanines , Zinc
Language: English
Type: Thesis , Masters , MSc
Identifier: vital:4374 , http://hdl.handle.net/10962/d1005039 , Photochemotherapy , Electrochemistry , Phthalocyanines , Zinc
Description: The synthesis of symmetrically and unsymmetrically substituted zinc phthalocyanines (ZnPc) derivatives is done according to reported procedures. The unsymmetrical ZnPc derivatives are synthesized by ring expansion of sub-phthalocyanine complexes. Ring substitution is effected with tert-butyl phenol, naphthol, and hydroxybenzoic acid. Comparison of the redox potentials for the complexes substituted with varying numbers of tert-butyl phenol: 1, 2, 3, 6 and 8 show that the complex with the highest number of substituents are more difficult to oxidize and easier to reduce. Water soluble sulphonated ZnPc (ZnPcSn) was prepared. The possibility of using axial ligation to increase the solubility and the photochemical activity of sulphotnated ZnPc in aqueous solutions was investigated. Pyridine, aminopyridyl and bipyridyl were used as axial ligands. When bipyridyl was used as the axial ligand, solubility of the ZnPcSn increased, shown by the increase in the Q-band of the monomer species in solution and the singlet oxygen quantum yields was relatively higher than that of the unligated ZnPcSn. The singlet oxygen quantum yields by the various complexes in DMF using diphenylisobenzofuran as a chemical quencher for organic solvent were determined. Singlet oxygen quantum yields for the unsymmetrically ring substituted complexes range from 0.22 to 0.68. Photobleaching quantum yields are in the order of 10-5, which means that the complexes are relatively photostable.
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Date Issued: 2003

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Bayliss-Hillman adducts as scaffolds for the construction of novel compounds with medicinal potential

- Idahosa, Kenudi Christiana

Authors: Idahosa, Kenudi Christiana
Date: 2012
Subjects: Antimalarials -- Research Malaria -- Chemotherapy -- Research AIDS (Disease) -- Treatment -- Research AIDS (Disease) -- Chemotherapy -- Research
Language: English
Type: Thesis , Doctoral , PhD
Identifier: vital:4410 , http://hdl.handle.net/10962/d1006763
Description: This project has focused on exploring the application of Baylis-Hillman (BH) {a.k.a. Morita-Baylis-Hillman (MBH)} scaffolds in the construction of various compounds with medicinal potential. A series of 2-nitrobenzaldehydes has been treated under BH conditions, with two different activated alkenes, viz., (MVK) and methyl acrylate, using (DABCO) or (3-HQ) as catalyst. While most of the BH reactions were carried out at room temperature, some reactions were conducted using microwave irradiation. The resulting BH adducts have been subjected to dehydration, conjugate addition and allylic substitution to obtain appropriate intermediates, which have been used in turn, to synthesize possible lead compounds, viz., cinnamate esters as HIV-1 integrase inhibitors, 3-(aminomethyl)quinolines and quinolones as anti-malarials and cinnamate ester-AZT conjugates as dual-action HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. Conjugate addition reactions of methyl acrylate-derived BH β-hydroxy esters with the amines, piperidine, propargylamine and 2-amino-5-(diethylamino)pentane, has afforded a range of products as diastereomeric mixtures in moderate to excellent yields. Catalytic hydrogenation of the aminomethy β-hydroxy esters derivatives, using a palladium-oncarbon (Pd-C) catalyst, has afforded the corresponding, novel 3-aminomethyl-2- quinolone derivatives in moderate yields. Effective allylic substitution reactions of the MVK-derived BH β-hydroxy ketones (via a conjugate addition-elimination pathway) using in situ-generated HCl has afforded the corresponding α-chloromethyl derivatives, which have been reacted with various amines, including piperidine, piperazine, propargylamine and 2-amino-5-(diethylamino)pentane, to yield α-aminomethyl derivatives. Catalytic hydrogenation of selected α-aminomethyl derivatives, using a Pd-C catalyst, has afforded the corresponding, novel 3- (aminomethyl)-2-methylquinoline derivatives in low to moderate yields. A bioassay, conducted on a 6-hydroxy-2-methyl-3-[(piperidin-1-yl)methyl]quinoline isolated early in the study indicated anti-malarial activity and prompted further efforts in the synthesis of analogous compounds. Reaction of the methyl acrylate-derived BH adducts with POCl3 has provided access to α-(chloromethyl)cinnamate ester derivatives, which have been aminated to afford α- (aminomethyl)cinnamate ester derivatives as potential HIV-1 integrase inhibitors. The α- (propargylaminomethyl)cinnamates were used, in turn, as substrates for the “click chemistry” reaction with 3'-azido-3'-deoxythymidine (AZT– an azide and an established reverse transcriptase HIV-1 inhibitor) to afford cinnamate ester-AZT conjugates as potential dual-action HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. Computer modelling and docking studies of a cinnamate ester-AZT conjugate into the HIV-1 integrase and reverse transcriptase active-sites revealed potential hydrogen-bonding interactions with amino acid residues within the receptor cavities. The isolated products have been appropriately characterized using IR, 1- and 2-D NMR and HRMS techniques, while elucidation of the stereochemistry of the double bond in the BH-derived halomethyl derivatives has been assigned on the basis of NOE, computer modelling and X-ray crystallographic data.
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Date Issued: 2012

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Design, synthesis and evaluation of novel, metal complexing agents

- Hagemann, Justin Philip

Authors: Hagemann, Justin Philip
Date: 1997
Subjects: Ligands Metal complexes
Language: English
Type: Thesis , Doctoral , PhD
Identifier: vital:4307 , http://hdl.handle.net/10962/d1004965
Description: Various chelating ligands have been designed and synthesised; these include amino-amide ligands, tetraacetic acid systems and sulfur-containing amide ligands. Difficulties in the synthesis and purification of the amino-amide ligands were largely overcome, permitting the mono acylation of ethylenediamine and the synthesis of bis(2-aminoethyl)-2-benzylpropanediamide. Novel tetraacetic acid ligands, based on the propanediamide backbone and targeted as EDTA analogues, were obtained from their methyl and benzyl esters; but the instability of the tetraacids prevented their full characterisation. Bidentate, tridentate and tetradentate sulfur-containing monoamide ligands, based on the ortho-thio acetanilide moiety, were designed to specifically chelate platinum and palladium in the presence of base metals. In their synthesis, thiocyanation was used to introduce the orth-thio group on para-substituted anilines, and further functionalisation was achieved via appropriate protection of nucleophilic sulfur moieties. A range of tetradentate, sulfur-containing diamide ligands was also synthesised by reacting substituted 2-mercaptoacetanilides with 1,2- dibromoethane. Novel ligands were characterised by spectroscopic (¹H and ¹³C NMR; IR and M S) techniques and elemental (combustion and high resolution MS) analysis. Computer modelling and ¹H NMR chemical shift data have been used to explore the conformational preferences of the sulfur-containing acetanilide ligands. The macrocyclic ligands and systems with ortho-methylthio substituents appear to exhibit the greatest degree of coplanarity of the aromatic and amide functions. Solvent extraction studies revealed that the sulfur-containing amide ligands selectively extracted palladium(II) from platinum(II), copper(II}, nickel(II} and cobalt(II}. Even though the palladium(II} was extracted from an acidic medium, certain monoamide ligands were able to complex palladium(II) through their sulfur and deprotonated amide nitrogen donors, a trithia monoamide ligand being observed to displace all the chloride ligands on palladium to form a monomeric tetracoordinate complex. The diamide ligands, however, appeared to favour extraction of palladium(II) by coordination through their sulfur donors, forming 5-membered sulfur-sulfur chelates. In basic media (pH 8-9), selected sulfur-containing monoamide and diamide ligands have been shown to complex platinum(II) and palladium(II) through their sulfur and deprotonated amide nitrogen donors. At neutral pH, a dimercapto monoamide ligand has been shown to complex platinum from cisplatin with partial expulsion of the ammine ligands, while a macrocyclic trithia monoamide ligand has been observed to complex platinum from tetrachloroplatinate with concomitant deprotonation of the amide nitrogen. Where possible, the complexes were characterised by infrared and ¹H NMR spectroscopy and have also been studied using the computer modelling soft-ware programmes, Momec® and Hyperchem®.
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Date Issued: 1997

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