The present study was undertaken with the view to evaluate methodologies based on traditional Scheffé experimental designs that study mixtures as a tool for discovery research particularly when seeking new and or improved uses of existing mixtures. For the purpose of this study, the topic of controlling the problematic weed known as Yellow Nutsedge (Cyperus esculentus L. var. esculentus) or “Geel Uintjie”, was selected on a rather ad hoc basis. Yellow Nutsedge is a troublesome perennial weed found in most agricultural countries in the world. Herbicidal control is often difficult because of the weeds’ ability to propagate via tubers, which can remain dormant for a number of years and are also resistant to most synthetic herbicide controls. As a first step the study involved the selection of a group of chemical compounds that would be used in suppressing the germination of Yellow Nutsedge tubers. Treatment with various combinations of these chemical compounds as determined by statistical experimental designs was carried out. A review of the literature, particularly literature concerned with the study of the phenomenon of allelopathy, suggested that various phenolic-D-glucopyranosides could show promise in the suppressing the germination of Yellow Nutsedge tubers. This led to the selection of this group of compounds as the target group of “active” substances for the study. Since the group of phenolic-D-glucopyranosides is quite large, and in order to keep the study to a reasonable size, only four phenolic-D-glucopyranosides were selected namely: 4-nitrophenyl-D-glucopyranoside, 4-chlorophenyl--Dglucopyranoside, arbutin and salicin. This selection was based firstly based on a particular phenolic-D-glucopyranoside being a suspected allelochemical, and secondly the ease of technical synthesis using a catalytic process. In addition to the four selected phenolic-D-glucopyranosides, their aglycones (4,nitrophenol, 4,chlorophenol, hydroquinone and salicyl alcohol) were also included as potential “active” substances in order to discern any potential activity between the phenolic-D-glucopyranosides and the aglycones. iii The selected “active substances” were combined in various combinations according to various mixture designs in such a manner that the sum of the proportions of the various actives in any one mixture was always equal to 1. The mixtures of actives were then used in various germination experiments and three experimental responses were measured namely the germination, average dry mass and length of longest shoot. From the results of these germination studies the canonical form of the polynomial equation describing the variation in each of the three germination responses was calculated and evaluated statistically. These equations were then used to estimate the presence of, and the magnitude of synergism between the various active substances. The results from these screening experiments and their detailed statistical analysis indicated that the response surface model for the germination response contains three synergistic blends (4-nitrophenyl--D-glucopyranoside + arbutin; 4-nitrophenyl--Dglucopyranoside + hydroquinone; and 4-chlorophenyl--D-glucopyranoside + salicin) and one antagonistic blend (4-nitrophenyl--D-glucopyranoside + 4- chlorophenol--D-glucopyranoside). The response surface model for the average dry mass response contains two synergistic blends (4-nitrophenyl--Dglucopyranoside + hydroquinone; and 4-chlorophenol--D-glucopyranoside + salicin) and the same antagonistic blend as for germination response. For both germination and average dry mass responses, the most synergistic blend was found to be the combination of 4-chlorophenyl--D-glucopyranoside and salicin. Two additional tests were conducted and both confirmed the results obtained from the screening designs. These tests involved the identification of the two components responsible for the synergistic activity that resulted in the suppression of the germination of the tubers and growth of the seedlings. The experimental response measuring the longest shoot proved to be erroneous and was excluded from the statistical analysis. In summary, this study has clearly shown that statistically designed experiments based on mixture designs can be used as a powerful tool in identifying and quantifying synergistic (or antagonistic) effects of chemicals on the germination ability of plant seeds.

The citrus industry is one of South Africa's largest agricultural sectors in terms of export earnings with lemon fruits and juice as a trendsetter due to their high grade quality. According to growers, the Eastern Cape Province of South Africa alone produces an excess of about 10-14,000 tons of lemon juice which is presently of no economic value due to the sour taste and “bitterness”. As a result of this excess and in order to make use of the polyprotic acids naturally occurring in the lemon juice, four fertilizer nutrient mixtures are formulated, using lemon juice as base. From a conceptual scientific approach, characterization (physico-chemical and functional properties determinations) of Eureka Lemon fruit juices were undertaken, followed by smaller scale batch formulation experiments. On the basis that these lemon juice-based fertilizer mixtures are prepared following standard liquid fertilizer formulation guidelines, a field test was conducted to evaluate their potential effectiveness to influence plant growth. A growth chamber testing on tomato plants revealed high growth response (> 99.9 % certainty) potential in two of the semi-organic mixtures formulated while the organic mixture showed a relatively good growth rate as compared to the control (pure tap water). According to statistical analysis (ANOVA) comparison, two of the semi-organic mixtures performed considerably better than the two commercial samples evaluated. Potential benefits profoundly associated with these nutrient mixtures as compared to similar liquid fertilizer products on the market is that most nutrients are chelated and dissolved in solution. Also, the mixtures contain all necessary nutrients including plant growth substances required for healthier plant growth. The most important socioeconomic impact is the value addition to the technology chain in the citrus industry. The use of fluid fertilizers in significant quantities is less than twenty years old. Nevertheless, growth has been so rapid that in South Africa demand for mixed liquid fertilizer has greatly increased from 90 000 tons NPK & blended micronutrients in 1955 to more than 600 000 per annum tons today (Report 41/2003, Department of Minerals and Energy). The liquid fertilizers market is sparsely specialized with major competitors like Omnia, Kynoch and Foskor supplying more than 50 % of the market demand. Amongst the nutrient mixtures formulated, mixture one is an NPK (1-1-2) based nutrient mixture containing both secondary nutrients (0.5 % Mg & 1.0 % Ca) and seven micronutrients (0.1 % Fe, 0.05 % Cu, 0.05 % Zn, 0.05 % Mn, 0.02 % B, 0.0005 % Mo and 0.0005 % Co). The composition of this mixture offers the formula a potential to be used as a general purpose (all stages of plant growth) fertilization mixture in view of its balanced composition (containing all essential plant nutrients). Mixture two contains essentially the micronutrients and in higher concentrations (0.3 % Fe, 0.3 % Cu, 0.1 % Zn, 0.2 % Mn, 0.02 % B, 0.0005 % Mo and 0.0005 % Co) as compared to mixture one except for boron, molybdenum and cobalt. The concentration of the micronutrients contained in this mixture is adequately high which offers a potential for it to be used in supplementing nutrition in plants with critical micronutrient-deficient symptoms. Mixture three is very similar to mixture two (1.0 % Fe, 0.05 % Cu, 0.05 % Zn, 0.05 Mn, 0.05 % B, 0.0005 % Mo and 0.0005 % Co) except that the concentrations of all seven micronutrients are considerably less than those of contained in mixture two. However, the concentration of iron in this mixture is as high as 1.0 %. The mixture has a potential to be used in high iron-deficient situations. Mixture four is an organic formula with relatively low nutrient concentrations (NPK-0.02-0.02-1, 0.27 % Mg, 0.02 % Ca, 0.008 % Fe, 0.26 % Cu, 0.012 % Zn, 0.009 % Mn). Nevertheless, this mixture is appealing for organically grown crops where the use of chemicals is prohibited by standards. These lemon juice-based nutrient mixtures were further characterized and tested for stability and storability over a period of eight weeks. This study revealed no major change in the physical quality (colour, pH and “salt out” effect). The basic formulation methodology is a two-step procedure that involves filtration of the lemon juice to remove membranous materials, mixing at ambient temperature and stabilization of the nutrient mixtures. However, for the organic nutrient formula mix, filtration follows after extraction of nutrients from plant materials using the lemon juice.

In this study a presentation of the technology behind dye-sensitized solar cells, their design as well as the role of the different parts of the cell. The characterization of the cell is divided into four sections namely: the characterization of the paste required to make the TiO2 film and its optical properties using SEM-EDX and XRD analytical techniques; Analysis of the various absorptions of three Ru-based dyes using UV-Vis spectroscopy, Photoluminescence and Fourier Transform Infra-Red spectroscopy; the characterization and the analyses of the entire cell using Electrochemical Impedance Spectroscopy. The nine cells were prepared by examining RuL2(CN)2 , RuL2(NCS)2 or N3 dye and RuL2(NCS)2 TBA+ or N719 dye. [L = 2,2'-bipyridyl-4,4'-dicarboxylic acid ;TBA = tetra-butyl ammonium] were combined with three electrolytes namely: Z–150 , AN–50 and PN–50. The Iodolyte PN–50 is an iodide based low viscosity electrolyte with 50 mM of tri-iodide dissolved in a solvent called propionitrile (PN). The Iodolyte AN–50 is an iodide based low viscosity electrolyte with 50 mM of tri-iodide dissolved in a solvent called acetonitrile (AN). The Iodolyte Z–150 is an iodide based low viscosity electrolyte with 150 mM of tri-iodide dissolved in a solvent called 3-methoxypropionitrile (MPN) and with additives such an ionic liquid, malkylbenziimidazole and guanidine thiocyanate. A solar simulator was utilized with which the standard solar irradiation can be created in laboratory conditions. The fill factors as well as overall performance efficiencies of the these cells are quite low < 1.0%,.

Biomass gasification has attracted the interest of researchers because it produces zero carbon to the atmosphere. This technology does not only produce syngas but also the byproducts which can be used for various application depending on quality.The study conducted at Melani village in Alice in the Eastern Cape of South Africa was aimed at investigating the possible applications of the gasification byproducts instead of being thrown away. Pine wood was employed as the parent feedstock material for the gasifier. Biomass gasification by-products were then collected for further analysis. The studied by-products included tar(condensate), char, soot and resin. These materials were also blended to produce strong materials.The essence of the blending was to generate ideal material that is strong but light at the same time.The elemental analysis of the samples performed by CHNS analyser revealed that carbon element is in large quantities in all samples. The FTIR spectra showed almost similar results for all the studied samples, since the samples are end products of lignocellulosegasification. SEM gave the sticky images of resin as well as porous char structures. Char showed a higher heating value of 35.37MJ/Kg when compared to other by-products samples.

Cymbopogon validus and Hyparrhenia hirta belong to the Poaceae botanical family. Both plants are used as thatching material; H. hirta is also used for weaving mats and baskets. In this study, we investigated the anti-inflammatory effects of C. validus and H. hirta essential oils on fresh egg-albumin induced edema on Wistar rats. To fully understand the chemically induced anti-inflammatory properties of these plants, we first analyzed the chemical composition of the essential oils. The essential oils were analyzed using gas chromatography-mass spectrometry (GC-MS). In C. validus, 13 compounds accounted for 74.3% of fresh leaves oil, 14 compounds 71.8% of dried leaves oil and 12 compounds 73.3% of flower oil were identified from the GC-MS Chromatogram. The percentage yields were as follows fresh leaves oil 2.2%, dried leaves oil 2.0% and flower oil 2.4% v/w respectively. Linalool (3.2-29.6%) and northujane (4.4-16.9%) were the dominant compounds found in the 3 oils analyzed. While, α-terpineol 37.5% and verbenone 13.5% was only found in the fresh leaf oil, this was absent in the dried leaves oil and the flowers oil of C. validus. In H. hirta, 25 compounds accounted for 68.1% of fresh leaves oil, 40 compounds 71.9% of dried leaves oil, 23 compounds 77.6% of fresh flowers oil and 18 compounds 80.1% of dried flowers oil were identified from the GC-MS Chromatogram. The percentage yields obtained from the different parts were 3.4% for fresh leaves oil, 2.8% for dried leaves oil, 2.8% for fresh flowers oil and 0.7% for dried flowers oil v/w respectively. Northujane (8.5-30.0%), diisooctyl phthalate (4.4-26.5%), phytone (1.1-10.4%) were the dominant compounds found in the 4 oils analyzed. While, dibutyl phthalate 26.9% was only found in the fresh flowers and was absent in the dried flowers oil. Moreover, caryophyllene oxide (1.7-9.6%) was found in fresh leaves and dried flowers oil of H. hirta. In vivo analysis revealed that the two essential oils displayed significant edema inhibition effect overtime. They displayed strong anti-inflammatory properties when compared to control group. However, the H. hirta essential oil was more effective than that of C. validus. Linalool, α-terpineol, and northujane extracted from C. validus and H. hirta essential oils might have contributed to the anti-inflammatory effects observed in Wistar rats. This study, confirms the anti-inflammatory properties of C. validus and H. hirta suggesting that they may be used in diseases related to anti-inflammation.

The research described in this dissertation was motivated by the global demand for energy that is not dependent on coal, oil, natural gas and other non-renewable fossil fuels. The technology used in this project is related to the use of biomass to produce a viable alternative to conventional sources of fuel. A bench scale biomass to liquid (BTL) facility was built and tested. This produced results confirming the feasibility of the BTL process. The findings of the pilot study outlined in this dissertation justified the conclusion that the next step will be to expand the capacity and productivity of the BTL pilot plant to an industrial scale. Biomass comes from a variety of renewable sources that are readily available. In this case, the material used in the fixed bed biomass gasification facility to generate wood gas was agricultural and forestry waste, such as straw and wood chips. The gasifier had the capacity to produce up to 10 cubic metres/hr of gas with a carbon monoxide and hydrogen content of between 20–40% by volume, when it was operated at ambient pressure and with air as the oxidizer. The gas, produced at a temperature above 700º C, was cooled in a quench/water scrubber in order to remove most of the mechanical impurities (tars and water-soluble inorganic particles), condensed and dried with corn cobs before being compressed in cylinders at over 100 bar (g) for use in the Fischer-Tropsch Synthesis (FTS). The syngas was subjected further to a series of refining processes which included removal of sulphur and oxygen. The sulphur removal technology chosen entailed applying modified activated carbon to adsorb H2S with the help of hydrolysis in order to convert organic sulphur impurities into H2S which reduced the sulphur content of the gas to less than 5 ppbv. Supported cobalt catalyst (100 grams), were loaded into a single-tube fixed bed FT reactor with an inner diameter of 50 mm. The reactor was fitted with a heating jacket through which, heated oil ran to cool the reactor during a normal reaction occurring at < 250 ºC, while nitrogen was used in the heating jacket during reduction, which occurred at temperatures up ~ 350 ºC. The FTS reaction was carried out at different pressures and temperatures. Liquid and wax products were produced from the facility. The properties of the liquid and solid hydrocarbons produced were found to be the same as FT products from other feed stocks, such as natural gas and coal.

Titanium dioxide nanoparticles were prepared using the sol-gel process. The effect of temperature and precursor concentration on particle size was investigated. The optimum conditions were then used to prepare carbon and nitrogen doped titanium dioxide (TiO2) nanoparticles. Doping was done to reduce band gap of the nanoparticles in order to utilize visible light in the photocatalytic degradation of organic compounds. A significant shift of the absorption edge to a longer wavelength (lower energy) from 420 nm to 456 nm and 420 nm to 428 nm was observed for the carbon doped and nitrogen doped TiO2 respectively. In this study, the prepared TiO2 photocatalyst was immobilized on carbon nanofibres to allow isolation and reuse of catalyst. The photocatalytic activity of the catalyst was tested using methyl orange as a model pollutant and was based on the decolourization of the dye as it was degraded. The doped TiO2 exhibited higher photocatalytic activity than the undoped TiO2. The materials prepared were characterized by XRD, TEM, SEM, FT-IR, DSC and TGA while the doped TiO2 was characterized by XPS, ESR and Raman Spectroscopy.

The aim of this study was to prepare composite materials based on titanium dioxide (TiO2) and silicon dioxide (SiO2), and to evaluate their photo-catalytic and antimicrobial properties. Carbon and nitrogen doped TiO2nano-particles were prepared via a sol gel synthesis, which is a simple hydrolysis and condensation technique. In situ doping was carried out using glucose and urea as carbon and nitrogen sources respectively. Doping increased the spectral response of titanium dioxide photo-catalyst, allowing it to utilise the visible region which is much wider than the UV region (about 40 % of the solar spectrum), thus making it a more efficient photo-catalyst. The carbon and nitrogen doped TiO2-SiO2nano-particles were immobilized on glass support material to allow for easy separation of the spent photo-catalyst after the photo-degradation process. Tetraethyl orthosilicate (TEOS) was employed as both a binder and precursor for silicon dioxide. A mixture of TiO2 and TEOS in a 1:1 ratio was allowed to polymerize on a glass support which had been treated with hydrofluoric acid to introduce OH groups. The prepared photo-catalytic material was characterized by FT-IR, XRD, DRS, TEM, EDX, and BET analyses. Carbon was found to be more effective as a dopant than nitrogen. It brought about a band gap reduction of 0.30 eV and a BET surface area of 95.4 m2g-1 on the photo-catalyst as compared to a gap reduction of 0.2 eV and surface area of 52.2 m2g-1 for nitrogen doped TiO2. On the other hand, introduction of SiO2 allowed utilization of visible light by the TiO2-SiO2 nano-composite leading to an improved rate of photo-degradation of both methyl orange and phenol red. However, the immobilization of TiO2 on support material made it less effective towards inactivation of E. coli ATCC 25922 bacterial cells when compared to powdered TiO2 which was able to inactivate about 98 % of the bacterial cells within an hour of treatment.

Syzygium cordatum Hoscht ex. C Krauss, also known as water berry, is normally used by the people of South Africa for respiratory ailments including tuberculosis, stomach complaints, treatment of wounds and as emetics. An extract of the leaves can be used as a purgative for diarrhoea treatment. The leaves of Syzygium cordatum Myrtaceae were obtained from the Eastern Cape Province of South Africa, air dried and sequential solvent extraction was done to obtain various non volatile crude extracts. The volatile extract, that is the essential oil was extracted from the leaves using hydrodistillation and analysis of compounds was done by GC/MS for composition. 32 compounds were obtained from the fresh leaves and 18 compounds were obtained from the dry leaves. The fresh oil contains caryophyllene (11.8 percent) and caryophyllene oxide (11.1 percent) as the main sesquiterpene component. α-Pinene(5.0 percent) was the only monoterpene compound identified in the fresh oil in substantial amount. The dry leaves oil had copanene (17.0 percent), β-Caryophellene (26.0 percent), cubenol (6.5 percent) and caryophellene oxide (14.2 percent) as the dominant constituent of the oil. Summary of the classes of compounds in the oil revealed that the chemical profile of both oils were dominated by sesquiterpenoid compounds. This is the first time that terpenoids compounds are being identified in both the fresh and dry leaf oil of S. cordatum. Hexane leaf extract was selected due to the interest in the terpenoid compounds. Column chromatography of the hexane crude gave five (5) of which two are fully reported. The isolates were fully elucidated using spectroscopic methods to be β-Sitosterol (HC3) and Friedela-3-one (HC1A/HC1D). Cytotoxicity analysis was carried out on the crude using the Brine shrimps assay. Isolates 1C and1D showed significant lethality using the brine shrimps assay with lethality values (LC50) of 4.105mg/ml for HC1C and 4.11mg/ml for 1D/1A respectively.

Some new acylpyrazolone Schiff bases have been synthesized from the condensation reaction of two acylpyrazolone diketone precursors with phenylhydrazine, 2,4-dinitrophenylhydrazine and sulfanilamide. They have been fully characterized by elemental analysis and spectroscopic techniques (IR,1H and 13C NMR, and mass-spectra). The single crystal structure of the benzoyl derivative acylpyrazolone Schiff bases have been obtained and analyzed by X-ray crystallography technique. Solid state X-ray diffraction revealed a keto tautomer Schiff base in solid state. Mn(II), Co(II), Ni(II) and Cu(II) complexes with the Schiff bases have been synthesized and characterized by elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility measurements, and thermal studies (TGA and DTG). An octahedral geometry around the transition metal ion, consisting of two bidentate Schiff base ligands bonding through the azometine nitrogen and ketonic oxygen have been proposed based on careful interpretation of available analytical and spectroscopic characterization results. Two water molecules as ligands complete the octahedral geometry in all cases. Using the invitro disc diffusion method for screening synthesized compounds against selected gram positive and gram negative bacterial at 40 mg/mL, and the DPPH free radical scavenging methods at 0.50, 0.25 and 0.13 mg/mL, the synthesized Schiff base and metal complexes showed varying biological activities. 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one sul29 fanilamide showed more activity generally, exhibiting a broad spectrum activity against all selected bacterial in some cases. Mn(II), Co(II) and Ni(II) complexes of sulfanilamide Schiff base with the acetylpyrazolone derivative 4-acetyl-3-methyl-1-phenyl-2-pyrazolin-5-one sulfanilamide, exhibited a stronger and very good DPPH radical scavenging activity as good as ascorbic acid on comparing, but not with Cu(II). As such they could be important antitumour candidates.