The solubility of barium sulphate in water at 25°
- Authors: Rosseinsky, D R
- Date: 1957
- Subjects: Chemistry, Physical and theoretical , Solubility , Barium sulfate
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4491 , http://hdl.handle.net/10962/d1013097
- Description: Barium sulphate is a widely used analytical precipitate and for this reason its properties have been extensively studied. The variety of results encountered with barium sulphate samples prepared by different methods is an indication of the complex nature of this interesting substance. Intro., p. 8.
- Full Text:
- Date Issued: 1957
A comparative kinetic study of the reaction between chromium nitrate solutions and the carboxyl groups of acetate and collage
- Authors: Russell, Allan Edward
- Date: 1962
- Subjects: Chemical kinetics , Chromium , Spectrophotometry , Electrophoresis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4493 , http://hdl.handle.net/10962/d1013101
- Description: The kinetics of the coordination reaction between the carboxyl group of the acetate radical and the trivalent chromium ion has been examined by independent methods at a temperature selected to yield reasonably accurate rate data. The study has been extended to an examination of the rate of chromium "fixation" by the carboxyl groups of hide collagen in a series of miniature tannages carried out under similar conditions for comparative purposes. The effect of olation of the chromium ions in solution on the kinetics of t he coordination reaction has also been examined. The rate of coordination of the acetate radical was followed by solvent extraction and spectrophotometric techniques over a range of concentration and pH levels. The rate data revealed a reaction having typical mass-action characteristics, the rate of reaction depending on the concentration levels of the chromium ion and the ionised acetate radical. An attempt made to distinguish a differential reaction rate in the case of a parallel reaction series using boiled and aged chromium nitrate reactant solutions, failed to reveal any significant differences between the series. The reactant solutions gave absorption spectra characteristic of the trivalent chromium ion with maxima in the 420 mµ and 570 mµ wavelength regions. The changes in optical density occurring in the vicinity of the maxima were followed spectrophotometrically, the height of the 570 mµ being found to increase during the course of reaction, while the height of the 420 mµ peak decreased. The variation in optical density at the 570 mµ peak was found to be directly related to the increase in concentration of the product complex in solution in accordance with the Baer-Bougher law, while the decrease in the height of the 420 mµ peak was related to the properties of unolated OH groups associated with the chromium complex as governed by pH and olation changes during the course of reaction. Boiled and aged chromium nitrate solutions gave reactant solutions having initial optical densities greater than those of the correspending fresh reactant solutions at the 570 mµ peak, and less than those of the fresh solutions at the 420 mµ peak. During the course of reaction, however, the two series converged to the same values. The equilibrium reaction solutions were subjected to paper electrophoretic study which indicated that all tho chromium was present in the form of cationic species. This finding was in accordance with stoicheiometric indications in the solvent extraction studies where coordination in a l : 1 ratio was reflected, giving rise to positively charged complex ions only. Making due allowance for band spreading the numbers of species predicted from the kinetic studies correspond with the electrophoretic patterns found. Application of the classical second order kinetic expression to the solvent extraction rate data, yielded plots having two distinctly linear sections, apparently indicating consecutive second order processes occurring in solution, contrary to the findings of previous workers who assign a first order mechanism to the reaction. This finding was consistent with the view that in the case of both the fresh and aged series, reaction consisted of successive coordination of an acetate radical to each chromium atom of a diol complex. Second order rate "constants" were calculated for each step and their dependency on pH level demonstrated. The findings of Hamm et al that these were first order reactions independent of acetate co'ncentration are believed to be due to their use of a large excess of acetate in their experiments. The kinetic study was further extended to an examination of the rate of "fixation"of trivalent chromium by the carboxyl groups of hide collagen under comparable conditions in a series of miniaturv tanning experiments in which the tannage substrate was provided in each of two physical forms:- (a) As hide powder where surface development was large, and (b) as prepared pelt pieces in which the fibrous weave pattern was retained. In view of the heterogeneity of the tannage systems, remarkable similarity was observed in the reaction course when compared with that of the acetate coordination studies, particularly in the case of the hide powder tannages. The dependency of the tannage rate data upon concentration and pH conditions was also found to be the same as in the case of the pure chemical system. The exact correlation between the rate data for the tannage and pure chemical systems was demonstrated by means of correlation plots. Close correlation was revealed in the case of hide powder tannage while the smaller degree of correlation observed in the case of the pelt tannage systems was attributed to the modifying effects of diffusion, particularly on the initial reaction velocity. The effect of using boiled and aged chromium solutions in the tannages was to increase the initial rate of chroniill!l "fixation" apparently due to tho coordination of a dial species at each coordination site. After the initial reaction period, the two series showed a tendency to converge as in the case of the spectrophotometric studies on the acetate reaction. The convergence trend was regarded as indicative of the tendency for the chromium in fresh solutions to under go rapid olation to the ame level as in the boiled and aged solutions. The experimental observations made on the various systems lead to the following conclusions:- (a) The mechanism of coordination of the acetate radical ttrivalent chromium appears to involve the successive coordination of ligand to each of the chromium atoms of a diol complex, both coordination steps proceeding by second order reaction mechanisms. (b) At the pH levels at which the reaction is carried out, the formation of elated bodios is rapid so that reaction in the case of both fresh and aged solutions essentially occurs between an elated species and the ionised acetate radical. (c) Modificati0ns in the absorption spectrum of the reactant solution at the 570 mµ peak are directly related to coordination, while changes at the 420 mµ peak are related to the formation of loosely-bound hydroxo chromium compounds, the concentrations of which depend on the pH level. (d) The mechanism of chromium fixation in hide is essentially similar to that operating in the case of coordination of the acetate radical to chromium, involving attachment of chromium to the side chain acid r sidues of collagen. (e ) The effect of olation is to enhance the rate of chromium fixation by hide protein during the initial reaction stages and to render possible bridge formation between adjacent side chains by secondary coordination during the latter reaction stages. (f) Where pelt pieces are used instead of hide powder, the initial rate of chromium fixation is dominated by the rate of diffusion of chromium into the fibrous structure. It should be stressed that the observations made on the various reaction systems cannot be regarded as exhaustive and the conclusions are subject to further confirmation. Consequently, the present study is essentially of a preliminary nature, but it is felt that the need for further investigation along similar lines has been demonstrated.
- Full Text:
- Date Issued: 1962
Attempted synthesis of a [beta] or [gamma] resorcinyl alcohol
- Authors: Ryding, William Wallace
- Date: 1952
- Subjects: Alcohol -- Synthesis , Resorcinol
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4517 , http://hdl.handle.net/10962/d1014134
- Description: The ultimate objective of this research is the elucidation of the mechanism of the resorcinol-formaldehyde condensation. Whilst a vast literature has been built up about the phenol- formaldehyde condensation, that of resorcinol has received but scant attention, probably because the high reactivity of resorcinol rendered the following of the condensation extremely difficult. The earliest observation concerning the resorcinol-formaldehyde condensation was due to Baeyer who, in 1872, condensed resorcinol with various aldehydes. When the aldehyde was relatively inactive crystalline compounds were obtalned but with acetaldehyde or formaldehyde a resinous product resulted. In 1892 Caro condensed an excess ot resorcinol with formaldehyde in the presence of dilute hydrochloric acid; the product obtained recrystallised from alcohol as white microsoopic crystals, decomposed without melting at 250° and was stated to be bis (2- 4 dihydroxyphenyl) methane ... In decidlng upon the most suitable lines of attack it would seem that a survey of the literature relating to the phenol-formaldehyde concentration which might be expected to be closely related to that of resorcinol, would be of value. Summary of p. 1-5
- Full Text:
- Date Issued: 1952
An investigation of the orientation of certain long-chain fatty acids at the air-water interface
- Authors: Saayman, Henry Martin
- Date: 1962
- Subjects: Fatty acids , Surface chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4496 , http://hdl.handle.net/10962/d1013117
- Description: The results obtained for the cross-sectional areas of the series of long-chain fatty acids may best be summarized with the aid of Graph 9. This graphical representation of the molecular areas, in Ų , against the chain length (n), of the fatty acid molecules, illustrates variation of the areas with chain length for the series in recrystallized form, and also for selected samples in the zone purified and vacuum distilled forms. On the graph, the limits of variation of the molecular areas have been represented as lines of a length corresponding to twice the standard deviation (2S). This is to give representation that the standard deviation may be positive or negative in relation to the mean. For molecules with n odd and lying between 15 and 19, the molecular area decreases. This may be due to the effect of 3 factorsg (1) A general decrease in lateral translation because of the increasing molecular mass (translational kinetic energy per molecule = ½ mc ⁻²), resulting in closer spacing of molecules. (2) A general, but steady decrease in the angle of tilt of the molecules which thus tend to be held more erect in the condensed film. (3) A general decrease in the precessional motion of the hydrophobic chain groups. For molecules with n odd and between 19 and 23, the molecular areas increase probably due to the steady increase in molecular mass causing the long chains to commence to buckle, tilt or topple in their upper regions. This tilting becomes greater because of the increasing gravitational effect on the heavier molecules which tends to make them assume a flatter posture in relation to the surface. The lower values observed for margaric and nonadecanoic acids, may be due to increasing symmetry in the chain, with corresponding economy in packing in condensed monolayers. This effect may be connected with increasing cylindrical symmetry of the hydrocarbon chain for even values of n. The results of this investigution, incomplete as it is, - serve to indicate what might reasonably be expected to happen in the orientation of these fatty acids in monolayers. Further work, especially on a greater range of acids with even n, is clearly necessary in order to establish the tentative ideas which have been suggested. However, in the present research, work was limited to those acids in the series which were obtainable without undue difficulty or delay, those which would spread readily under the conditions of experiments carried out at 20°C, and those which could be purified relatively easily. The acids below n = 15 in the series were found to be too soluble in aqueous substrates, at operating temperatures of 20°C, to yield reliable evidence with the Langmuir trough technique. The acids above n = 23 were unobtainable commercially and the synthesis of those acids from the lower members in the series presented problems of isolating the required specimens and difficulty in purifying these, which were considered b be beyond the scope of the present research. Summary and conclusion, p. 122.
- Full Text:
- Date Issued: 1962
Investigation leading to a process for the synthesis of hydrogen sulphide from sulphur and certain lubricating oils derived from petroleum
- 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.
- Full Text:
- Date Issued: 1952
Synthesis of triprenylated toluquinone and toluhydroquinone metabolites from a marine-derived Penicillium fungus
- Authors: Scheepers, Brent Ashley
- Date: 2007
- Subjects: Penicillium , Antineoplastic agents , Marine fungi , Quinone
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4373 , http://hdl.handle.net/10962/d1005038 , Penicillium , Antineoplastic agents , Marine fungi , Quinone
- Description: This project forms part of a collaborative effort between the marine natural products chemists at Rhodes University and the medical biochemists at the University of Cape Town’s School of Medicine. Our UCT collaborators tested the cytotoxicity of a group of toluhydroquinones and toluquinones (9-15) against the oesophageal cancer cell line WHCO1 and revealed that the triprenylated toluhydroquinone 11 and it’s oxidised analogue 12 were the most active. This thesis presents an investigation into the role of the polyprenyl side-chain in the cytotoxicity of compound 11 and it’s oxidised analogue 12 by synthesizing and testing the cytotoxicity of simplified analogues of this compound. The synthesis of the two ortho-prenylated toluhydroquinone analogues 5-methyl-2-[(2'E,6'E)-3',7' -dimethyl-2',6'-octadienyl]-1,4-benzenediol (19) and 5-methyl-2-[(2'E,6'E)-3',7',11'-trimethyl-2',6',10'-dodecatrienyl]-1,4-benzenediol (21) and their two ortho-prenylated toluquinone analogues, 5-methyl-2-[(2'E,6'E)-3',7'-dimethyl-2',6'-octadienyl]-2,5-cyclohexadiene-1,4-dione (20) and 5-methyl-2-[(2'E,6'E)-3',7',11'-trimethyl-2',6',10'-dodecatrienyl]-2,5-cyclohexadiene-1,4-dione (22) is described. Our initial attempts to couple geranyl bromide, farnesyl bromide and farnesal to the aromatic precursors m-cresol and 1,4-dimethoxy-2-methylbenzene using directed ortho-prenylation and phenoxide carbon-alkylation were unsuccessful. The four target analogues were eventually synthesized via the initial metal halogen exchange reaction between 1-bromo-2,5-dimethoxy-4-methylbenzene and geranyl bromide/farnesyl bromide using n-BuLi and TMEDA in ditheyl ether at 0 °C to yield 92 and 104 respectively in moderate yield. The demethylation of both compounds preceded smoothly using AgO giving the target analogues 20 and 22 in good yield (approx. 90 %). The reduction of quinones 20 and 22 with sodium dithionite gave 19 and 21 in quantitative yield. The synthesis reported here is the first regioselective synthesis of these compounds. The anti-oesophageal cancer activity of 19-22 and two commercially available non-prenylated analogues 17 and 18 were tested against WHCO1. The conclusion drawn from the anti-oesophageal cancer study was that the polyprenyl side-chain plays a negligable role in the cytotoxicity of compounds such as 11 and 9 against the oesophageal cancer cell line WHCO1.
- Full Text:
- Date Issued: 2007
The exploitation of methane from landfill
- Authors: Schütte, Renate
- Date: 1992
- Subjects: Methane , Waste products as fuel , Refuse as fuel , Sanitary landfills -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4530 , http://hdl.handle.net/10962/d1015949
- Description: A review of literature on the subject of methane exploitation from landfill is presented in conjunction with the results of experiments concerning landfill gas extraction at the Grahamstown Landfill Site. A description of the LFG extraction system and the utilisation of LFG at the Grahamstown Landfill Site is included. Data concerning LFG enhancement parameters, LFG compositions and flow rates, refuse composition, LFG modelling, LFG pumping trials and the economics of LFG extraction and utilisation are presented. The indication is that LFG can be economically extracted and utilised as a heating fuel in South Africa.
- Full Text:
- Date Issued: 1992
The thermodynamics of binary liquid mixtures
- Authors: Scoones, Brett Warren Hamilton
- Date: 1983 , 2013-03-15
- Subjects: Thermodynamics , Thermodynamics -- Tables , Solution (Chemistry) , Liquids
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4392 , http://hdl.handle.net/10962/d1005893 , Thermodynamics , Thermodynamics -- Tables , Solution (Chemistry) , Liquids
- Description: A systematic study of the excess thermodynamic properties of two-ring compounds and n-alkanes was conducted. The excess enthalpies were determined at 288,15 K and 298,15 K by using a flow microcalorimetric technique. The excess volumes of tetralin and cycloalkanes, and tetralin and --alkans at 288,15 K and 298,15 K were determined by using a vibrating tube densitometer. The results showed trends relating to the size and shape of the n-alkane and cycloalkan molecules. The theory developed by Flory was applied to the decalin + cycloalkane and + n-alkane systems and this gave qualitative predictions of the excess enthalpies from the excess volumes and vice versa. , KMBT_363 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 1983
Design, development and evaluation of novel lead compounds as HIV-1 enzyme inhibitors
- Authors: Sekgota, Khethobole Cassius
- Date: 2015
- Subjects: Enzyme inhibitors , Viruses -- Reproduction , HIV (Viruses)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4546 , http://hdl.handle.net/10962/d1017926
- Description: This project has been concerned with the application of the Baylis-Hillman methodology to the synthesis of medicinally important diketo acid analogues (cinnamate ester-AZT conjugates and 3-hydroxy ester-AZT conjugates) as dual-action HIV-1 IN/RT inhibitors; and on exploratory studies in the preparation of 3-(amidomethyl)-(1H)-2-quinolones as PR inhibitors; and (1H)-2- quinolone-AZT conjugates as dual action IN/RT inhibitors. A series of Baylis-Hillman adducts has been prepared, typically in moderate to excellent yield, by reacting 2-nitrobenzaldehyde with methyl acrylate, ethyl acrylate and methyl vinyl ketone in the presence of 1,4- diazabicyclo[2.2.2]octane (DABCO). Subsequently, various transformations that include conjugate addition of primary and secondary amines to the α,ß-unsaturated moiety to obtain 2- (aminomethyl)-3-hydroxy-3-(2-nitrophenyl)propanoate derivatives, effective SN2´ substitution of the BH ß-hydroxy by a Vilsmeier-Haack in situ-generated chloride to afford Baylis-Hillman allyl chlorides, iron in acetic acid-catalyzed cyclisation to 3-acetoxymethyl-(1H)-2-quinolone derivatives were achieved. Thus, using the Baylis-Hillman methodology, two nuanced classes of diketo acid analogues were constructed. These involved conjugating appropriate propargylamine derivatives with AZT using the „click‟ reaction. In an exploratory study, the quinolone derivative, precisely 3-acetoxymethyl- (1H)-quinol-2-one, was transformed into 3-hydroxymethyl-(1H)-quinol-2-one using potassium carbonate in a mixture of methanol and water (1:1). Following successful hydrolysis, the resulting alcohol was transformed to the corresponding chloride, 3-chloromethyl-(1H)-quinol-2- one, using thionyl chloride. Subsequent nucleophilic substitution afforded 3-(aminomethyl)- (1H)-2-quinolone derivatives which were subsequently transformed to 3-(amidomethyl)-(1H)-2- quinolones; and 3-[(propargylamino)-methyl]-(1H)-quinol-2-one as precursors to quinolone- AZT derivatives. All compounds were characterized by NMR, IR, and where appropriate, high resolution MS
- Full Text:
- Date Issued: 2015
Photophysical properties of zinc carboxy phthalocyanine-quantum dot conjugates
- Authors: Sekhosana, Kutloano Edward
- Date: 2013 , 2013-03-27
- Subjects: Phthalocyanines , Quantum dots , Zinc , Photochemistry , Atomic force microscopy , Transmission electron microscopy , Raman spectroscopy , Infrared spectroscopy , X-ray photoelectron spectroscopy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4276 , http://hdl.handle.net/10962/d1001652 , Phthalocyanines , Quantum dots , Zinc , Photochemistry , Atomic force microscopy , Transmission electron microscopy , Raman spectroscopy , Infrared spectroscopy , X-ray photoelectron spectroscopy
- Description: This thesis presents work based on the interactions of water soluble caboxylated zinc phthalocyanines (Pcs) and coreshell quantum dots (QDs). The Pcs are ZnPc(COOH)₈ and ZnPc(COOH)₄ and coreshell QDs are CdTe@ZnS-GSH. GSH = L-glutathione. Characterization and photophysical studies of conjugates were carried out. The approach of coordinating Pcs to QDs was achieved using an organic cross linker, N-N’-dicyclohexylcarbodiimide (DCC) at pH 10 at room temperature. Employing atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman, infrared and X-ray photoelectron spectroscopies, the formation of the conjugates was confirmed. Upon conjugation with Pc derivatives, the fluorescence quantum yield of CdTe@ZnS-GSH decreased due to energy transfer from the QDs to the Pc. The average fluorescence lifetime of the CdTe@ZnS-GSH QD also decreased upon conjugation. The föster resonance energy transfer (FRET) behaviour of CdTe@ZnS-GSH-ZnPc(COOH)₄ conjugates was compared to that of CdTe@ZnS-GSH-ZnPc(COOH)₈. Higher FRET efficiencies were observed for CdTe@ZnS-GSH-ZnPc(COOH)₄-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₄-linked compared to the corresponding CdTe@ZnS-GSH-ZnPc(COOH)₈-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₈-linked. Triplet quantum yield (ΦT) and lifetime (ΤT) of ZnPc(COOH)₈ were found to increase in the presence of coreshell QDs. Though the singlet quantum yield (ΦΔ) value of ZnPc(COOH)8 was lower than ΦT , there was a slight upsurge in the ΦT in the presence of QDs. , Microsoft� Word 2010 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
Photosensitizing properties of non-transition metal porphyrazines towards the generation of singlet oxygen
- Authors: Seotsanyana-Mokhosi, Itumeleng
- Date: 2001 , 2013-05-02
- Subjects: Phthalocyanines , Photosensitization, Biological , Active oxygen -- Physiological effect , Photosensitizing compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4395 , http://hdl.handle.net/10962/d1006086 , Phthalocyanines , Photosensitization, Biological , Active oxygen -- Physiological effect , Photosensitizing compounds
- Description: Metallophthalocyanine complexes containing non-transition metals are very useful as sensitizers for photodynamic therapy, a cure for cancer that is based on visible light activation of tumour localized photo sensitizers. Excited sensitizers generate singlet oxygen as the main hyperactive species that destroy the tumour. Water soluble sensitizers are sought after for the convenience of delivery into the body. Thus, phthalocyanine (pc), tetrapyridinoporphyrazines (tppa) and tetramethyltetrapyridinoporphyrazines (tmtppa) with non-transition central metal atoms of Ge, Si, Sn and Zn were studied. First was the synthesis of these complexes, followed by their characterisation. The characterisation involved the use of ultraviolet and visible absorption spectroscopy, infrared spectroscopy, nuclear magnetic resonance spectroscopy, electrochemical properties and elemental analysis. Photochemical properties of the complexes were then investigated. Photolysis of these macrocycles showed two processes; -reduction of the dye and photobleaching, which leads to the disintegration of the conjugated chromophore structure of the dye. Photobleaching is the reductive quenching of the excited state of the sensitizers. The intensity of the quenching decreased progressively from tmtppa, tppa to pc metal complexes with photobleaching quantum yields, 6.6 x 10.5⁻¹, 1.8 x 10.5⁻¹ and 5.4 x 10⁻⁶ for Zntmtppa, Zntppa and Znpc, respectively. Efficiency of singlet oxygen sensitization is solvent dependent with very different values obtained for the same compound in different solvents, for example, 0.25 and 0.38 were observed as singlet oxygen quantum yields for Gepc complex in DMSO and DMF respectively. In DMSO the efficiency of ¹O₂ generation decrease considerably from pc to tppa and finally tmtppa. In water Getmtppa exhibits much higher singlet oxygen quantum yield, hence promising to be effective as a sensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2001
In vitro susceptibility of Staphylococcus aureus to porphyrin-silver mediated photodynamic antimicrobial chemotherapy
- Authors: Shabangu, Samuel Malewa
- Date: 2020
- Subjects: Porphyrins , Nanoparticles , Photochemotherapy , Drug resistance in microorganisms , Staphylococcus aureus
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167476 , vital:41484
- Description: This work reports on the syntheses and characterization of symmetrical and unsymmetrical porphyrin complexes namely, 5,10,15,20-tetra(4-pyridyl)-porphyrinato zinc(II) (1), 5,10,15,20-tetrathienyl porphyrinato zinc(II) (2), 5-(4-hydroxyphenyl)-10, 15, 20-tris(2-thienyl) porphyrinato zinc(II) (3), 5-(4-carboxyphenyl)-10,15,20-tris(pentafluorophenyl)- porphyrinato zinc(II) (4), 5-(4-carboxyphenyl)-10,15,20-triphenyl-porphyrinato zinc(II) (5) and 5-(4-carboxyphenyl)-10, 15, 20-tris(2-thienyl)-porphyrinato zinc(II) (6). The synthesis of silver nanoparticles (AgNPs) was also undertaken in this research work. Complexes 1, 2, 3 and 6 were linked to oleic acid/oleylamine functionalized nanoparticles via self-assembly and 4-6 were linked via covalent interaction through an amide bond to glutathione capped AgNPs. The effect of nature of bond along with symmetry were investigated, of interest were the five membered thienyl substituents. The photophysical and photochemical behaviour of the complexes and their conjugates with AgNPs were investigated in dimethylformamide. The porphyrin and AgNPs conjugates afforded an increase in singlet oxygen quantum yield. Complexes 1-6 and their conjugates were used for photodynamic antimicrobial chemotherapy of Staphylococcus aureus. The antimicrobial studies were done in two different concentrations of 0.36 and 2.0 μg/mL. The thienyl substituted porphyrin complexes and their conjugates gave better photodynamic activity as compared to phenyl analogues
- Full Text:
- Date Issued: 2020
Anisotropic copper oxide nanorods decorated with gold and palladium nanoparticles and their enzymatic properties
- Authors: Sicwetsha, Simbongile
- Date: 2021-04
- Subjects: To be added
- Language: English
- Type: thesis , text , Masters , MSc
- Identifier: http://hdl.handle.net/10962/178547 , vital:42949
- Description: Access restricted until April 2023. , Thesis (MSc) -- Faculty of Science, Chemistry, 2021
- Full Text:
- Date Issued: 2021-04
Structural studies on yeast eIF5A using biomolecular NMR and molecular dynamics
- Authors: Sigauke, Lester Takunda
- Date: 2015
- Subjects: Molecular dynamics , Reverse transcriptase , HIV (Viruses) , HIV infections , Eukaryotic cells , Yeast
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4547 , http://hdl.handle.net/10962/d1017927
- Description: Eukaryotic initiation factor 5A, eIF5A, is a ubiquitous eukaryotic protein that has been shown to influence the translation initiation of a specific subset of mRNAs. It is the only protein known to undergo hypusination in a two-step post translational modification process involving deoxyhypusine synthase (DHS) and deoxyhypusine hydroxylase (DOHH) enzymes. Hypusination has been shown to influence translation of HIV-1 and HTLV-1 nuclear export signals, while the involvement of active hypusinated eIF5A in induction of IRES mediated processes that initiate pro-apoptotic process have inspired studies into the manipulation of eIF5A in anti-cancer and anti-diabetic therapies. eIF5A oligomerisation in eukaryotic systems has been shown to be influenced by hypusination and the mechanism of dimerisation is RNA dependent. Nuclear magnetic resonance spectroscopy approaches were proposed to solve the structure of the hypusinated eIF5A in solution in order to understand the influence of hypusination on the monomeric arrangement which enhances dimerisation and activates the protein. Cleavage of the 18 kDa protein monomer by introduction of thrombin cleavage site within the flexible domain was thought to give rise to 10 kDa fragments accessible to a 600 MHz NMR spectrometer. Heteronuclear single quantum correlation experiments of the mutated isotopically labelled protein expressed in E. coli showed that the eIF5A protein with a thrombin cleavage insert, eIF5AThr (eIF5A subscript Thr), was unfolded. In silico investigations of the behaviour of eIF5A and eIF5AThr (eIF5A subscript Thr) models in solution using molecular dynamics showed that the mutated model had different solution dynamics to the native model. Chemical shift predictors were used to extract atomic resolution data of solution dynamics and the introduction of rigidity in the flexible loop region of eIF5A affected solution behaviour consistent with lack of in vivo function of eIF5AThr (eIF5A subscript Thr) in yeast. Residual dipolar coupling and T₁ relaxation times were calculated in anticipation of the extraction of experimental data from RDC and relaxation dispersion experiments based on HSQC measurable restraints.
- Full Text:
- Date Issued: 2015
The high pressure catalytic hydrogenation of the tannin of black wattle (Acacia mollissima Willd)
- Authors: Silk, M H
- Date: 1947
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:21132 , http://hdl.handle.net/10962/6528
- Description: From Introduction: The wattle industry in South Africa has, from its commencement in the middle of the last century, gradually assumed a position of increasing importance in the economic structure of the country. Apart from the provision of a valuable tanning extract for home use and for export, the tree itself has proved of considerable importance to the Union’s mining industries. In addition there would appear to be possibilities for the utilisation in the near future, of the raw ground bark and the wattle extract for the manufacture of a number of by-products, including certain types of plastics.
- Full Text:
- Date Issued: 1947
Synthesis of indium phthalocyanines for photodynamic antimicrobial chemotherapy and photo-oxidation of pollutants
- Authors: Sindelo, Azole
- Date: 2019
- Subjects: Phthalocyanines , Azo dyes , Indium compounds , Photochemotherapy , Nanoparticles , Photodegradation , Pollutants , Water -- Purification
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67581 , vital:29116
- Description: Indium (III) octacarboxyl phthalocyanine (ClInOCPc) alone and when conjugated to magnetic nanoparticles (MNP-ClInOCPc), 2(3),9(10),16(17),23(24)-octapyridylsulfanyl phthalocyaninato chloroindium (III) (ClInOPyPc) and its quaternized derivative 2(3),9(10),16(17),23(24)-octamethylpyridylsulfanyl phthalocyaninato chloroindium (III) (ClInOMePyPc) were synthesized. All Pcs were tested for both photodynamic antimicrobial chemotherapy (PACT) of an unknown water sample and photo-degradation of methyl red (MR). The singlet quantum yield (ΦΔ) for the ClInOCPc and MNP-ClInOCPc in PAN polymer fibers were 0.36 and 0.20 respectively using ADMA as a quencher in water. The photo-inactivation of bacteria in a water sample with unknown microbes was tested, with the MNP-ClInOCPc inactivating 90.6 % of the microbes and the ClInOCPc with 84.8 %. When embedded to the polymer, there was 48% bacterial clearance for ClInOCPc and 64% clearance for the MNP-ClInOCPc. The rate of degradation of MR increased with decrease of the MR concentration, with the MNP-ClInOCPc having the fastest rate. For ClInOPyPc and ClInOMePyPc, the singlet quantum yields were 0.46 and 0.33 in dimethylformamide (DMF), respectively. The PACT activity of ClInOMePyPc (containing 8 positive charges) was compared to those of 9(10),16(17),23(24)-tri-N-methyl-4-pyridylsulfanyl-2(3)-(4-aminophenoxy) phthalocyaninato chloro indium (III) triiodide (1) (containing 3 positive charges) and 2-[4-(N-methylpyridyloxy) phthalocyaninato] chloroindium (III) iodide (2) (containing 4 positive charges). When comparing ClInOMePyPc, 1 and 2, the largest log reduction for E. coli were obtained for complex 2 containing four positive charges hence showing it is not always the charge that determines the PACT activity, but the bridging atom in the phthalocyanine plays a role.
- Full Text:
- Date Issued: 2019
A critical evaluation of the analytical method used for the separation and estimation of copper and nickel
- Authors: Sismey, J E
- Date: 1948
- Subjects: Copper -- Analysis , Nickel -- Analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4519 , http://hdl.handle.net/10962/d1014335
- Description: [From Introduction]. This thesis deals with the determination of copper and nickel both separately and in each other's presence. The work is divided into two sections, one of which treats the subject from the theoretical side while the other contains an account of the practical work performed by the author. In the theoretical section, an attempt is made to summarise the better-known methods for the determination of copper and nickel, and at the same time, to incorporate such improvements, criticism and variations as have appeared in the literature. The subject is so vast that its summary in so short a space must necessarily be incomplete. Yoe and Server, for example, quote 111 references on the subject of the nickel-dimethylglyoxine with other ions. Only a fraction of the literature was available, and space permitted only a fraction of this to be abstracted in the following pages.
- Full Text:
- Date Issued: 1948
Phase equilibria in three component systems alcohol-hydrocarbon-water
- Authors: Siswana, Msimelelo Patrick
- Date: 1992
- Subjects: Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4327 , http://hdl.handle.net/10962/d1004988 , Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Description: The fuel industry in many parts of the world is blending alcohols with motor fuel either to extend the fuel or to improve its octane rating or both. Unfortunately alcohols are hygroscopic and as a result, water becomes a component of the fuel. This can lead to phase separation and the formation of a water-rich layer which could have serious corrosion consequences. In an attempt to understand the phase-splitting in alcohol-petrol-water blends, phase equilibria in ternary systems (alcohol-hydrocarbon-water) have been determined by experiment. The phase equilibria in these ternary systems are also discussed in terms of modern theories of liquid mixtures and the UNIQUAC theory is applied to the "ethanol + benzene + water" ternary system. The alcohols are all the C₁, C₂, C₃ and C₄ alcohols, and the hydrocarbons include those typically found in petrol, e.g. cyclohexane, benzene and substituted benzenes.
- Full Text:
- Date Issued: 1992
A critical investigation into the methods of determining sulphur in plant material
- Authors: Smith, Anthony John Hibbert
- Date: 1962
- Subjects: Plants -- Effect of sulfur on , Plants -- Nutrition , Sulfur
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4520 , http://hdl.handle.net/10962/d1014526
- Description: Although sulphur is one of the more abundant elements present in plants, its importance as a plant nutrient has been underestimated until comparatively recently. Scientific literature over the past few years, however, shows that interest in the determination of sulphur in natural waters, soil and plant materials has been renewed. Perhaps the main reason for the non-recognition of the importance of sulphur as a plant nutrient is the fact that sulphur-deficiency seldom occurs since sufficient sulphur is usually added to the soil in rainfall (particularly near industrial towns) to supply all the sulphur requirements of plants. In addition, sulphur is frequently present in fertilizers added to soils to counteract deficiency in other elements, especially phosphorus. Superphosphates, for example contain up to 60%, gypsum. Sulphur is also added to the soil in some instances in order to reduce the soil pH, the elemental sulphur being fairly readily oxidised in the soil to sulphuric acid. The organic fraction in the soil also contains sulphur. , [From Introduction]. Although sulphur is one of the more abundant elements present in plants, its importance as a plant nutrient has been underestimated until comparatively recently. Scientific literature over the past few years, however, shows that interest in the determination of sulphur in natural waters, soil and plant materials has been renewed. Perhaps the main reason for the non-recognition of the importance of sulphur as a plant nutrient is the fact that sulphur-deficiency seldom occurs since sufficient sulphur is usually added to the soil in rainfall (particularly near industrial towns) to supply all the sulphur requirements of plants. In addition, sulphur is frequently present in fertilizers added to soils to counteract deficiency in other elements, especially phosphorus. Superphosphates, for example contain up to 60%, gypsum. Sulphur is also added to the soil in some instances in order to reduce the soil pH, the elemental sulphur being fairly readily oxidised in the soil to sulphuric acid. The organic fraction in the soil also contains sulphur.
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- Date Issued: 1962
The kinetics and mechanism of the oxidation of chromium (III) chloride
- Authors: Sole, Kathryn Clare
- Date: 1989 , 2013-08-28
- Subjects: Chromium chloride--Oxidation
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4301 , http://hdl.handle.net/10962/d1004921 , Chromium chloride--Oxidation
- Description: The kinetic behaviour of anhydrous CrCl₃ in gaseous oxidising atmospheres has been examined in the temperature range 350 to 630°C in order to identify optimum reaction conditions and to establish the mechanism by which the reaction is controlled. The reaction under consideration is CrCl₃ (s) + ¾ O₂ (g) → ½ Cr₂O₃ (s) + ³/₂ Cl₂ (g). The main experimental techniques used were isothermal and programmed-temperature thermogravimetry, supplemented by scanning electron-microscopy, surface-area determinations and porosity measurements. The effects of sample pelletisation, gas flowrate, temperature, oxygen partial pressure, pellet porosity and the addition of other oxide species on the rate and extent of reaction have been studied. The reaction is shown to occur in a single step, starting at -350°C under non-isothermal conditions, and exhibiting a deceleratory rate over most of the reaction. Isothermal thermogravimetric curves were fitted to a number of kinetic rate expressions, and a series of statistical analyses used to identify the rate equation which best describes the experimental data. Supporting evidence was provided by scanning electron-microscopic examination of partially-reacted samples. It is concluded that the reaction is under chemical control, and that reaction occurs by means of a linearly-advancing reactant-product interface. The reaction kinetics can be described by a contracting-geometry rate expression. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 1989