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We report a novel fragmentation and functionalization method using a cyclic iminyl radical. Formation of this radical occurs by microwave heating under mild conditions and short reaction times. The reaction avoids the use of explosive or toxic radical initiators and propagating agents. This reaction is versatile, with the ability to install two functional groups that are ultimately derived from a ketone in the substrate precursor. A variety of radical traps capable of forming both carbon-carbon bonds and carbon-heteroatom bonds have been tested, and the products are obtained in good yields. We demonstrate the power of this reaction by functionalizing complex natural products.

Biofuels are becoming more attractive worldwide because of the high energy demands and the fossil fuel resources that are being depleted. Biodiesel is one of the most attractive alternative energy sources to petroleum diesel fuel and it is renewable, non toxic, biodegradable, has low sulphur content and has a high flash point. Biodiesel can be generated from domestic natural resources such as coconuts, rapeseeds, soybeans, sunflower, and waste cooking oil through a commonly used method called transesterification. Transesterification is a reaction whereby oil (e.g. sunflower oil) or fats react with alcohol (e.g. methanol) with or without the presence of a catalyst (e.g. potassium hydroxide) to form fatty acid alkyl esters (biodiesel) and glycerol. The high-energy input for biodiesel production remains a concern for the competitive production of bio-based transportation fuels. However, microwave radiation is a method that can be used in the production of biodiesel to reduce the reaction time as well as to improve product yields. Sunflower oil is one of the biodiesel feedstocks that are used in South Africa and is widely used in cooking and for frying purposes. This study aims to use microwave irradiation to reduce the energy input for biodiesel production. The effect of various reaction variables, including reaction time (10 – 60 seconds), microwave power (300 – 900 watts), catalyst (potassium hydroxide) loading (0.5 – 1.5 wt%) and methanol to oil molar ratio (1:3 – 1:9) on the yield of fatty acid methyl ester (biodiesel) was investigated. The quality of biodiesel produced was analysed by Gas Chromatography (GC), Fourier Transform Infrared Spectroscopy (FTIR) and viscometry. The FTIR results confirmed the presence of functional groups of the FAME produced during transesterification. The results showed that transesterification can proceed much faster under microwave irradiation than when using traditional heating methods. The interaction between the alcohol and oil molecules is significantly improved, leading to shorter reaction times (seconds instead of hours) and improved diesel yields. The highest biodiesel yield obtained was 98% at 1:6 oil-to-methanol molar ratio for both 1 wt% and 1.5 wt% potassium hydroxide (KOH) at a reduced reaction time (30 seconds). The chemical composition of FAME (biodiesel) obtained from different conditions i contained palmitic acid (C16:0), stearic acid (C18:0), oleic acid (C18:1) and 70% linoleic acid (C18:2). The physical properties (cetane number, viscosity, density and FAME content) of biodiesel produced met the SANS 1935 specification. The energy consumption was reduced from 1.2 kWh with the traditional transesterification to 0.0067 kWh with the microwave transesterification. Microwave irradiation was shown to be effective in significantly lowering the energy consumption for production of biodiesel with good quality for small scale producers. / Thesis (MSc (Engineering Sciences in Chemical Engineering))--North-West University, Potchefstroom Campus, 2013

Biofuels are becoming more attractive worldwide because of the high energy demands and the fossil fuel resources that are being depleted. Biodiesel is one of the most attractive alternative energy sources to petroleum diesel fuel and it is renewable, non toxic, biodegradable, has low sulphur content and has a high flash point. Biodiesel can be generated from domestic natural resources such as coconuts, rapeseeds, soybeans, sunflower, and waste cooking oil through a commonly used method called transesterification. Transesterification is a reaction whereby oil (e.g. sunflower oil) or fats react with alcohol (e.g. methanol) with or without the presence of a catalyst (e.g. potassium hydroxide) to form fatty acid alkyl esters (biodiesel) and glycerol. The high-energy input for biodiesel production remains a concern for the competitive production of bio-based transportation fuels. However, microwave radiation is a method that can be used in the production of biodiesel to reduce the reaction time as well as to improve product yields. Sunflower oil is one of the biodiesel feedstocks that are used in South Africa and is widely used in cooking and for frying purposes. This study aims to use microwave irradiation to reduce the energy input for biodiesel production. The effect of various reaction variables, including reaction time (10 – 60 seconds), microwave power (300 – 900 watts), catalyst (potassium hydroxide) loading (0.5 – 1.5 wt%) and methanol to oil molar ratio (1:3 – 1:9) on the yield of fatty acid methyl ester (biodiesel) was investigated. The quality of biodiesel produced was analysed by Gas Chromatography (GC), Fourier Transform Infrared Spectroscopy (FTIR) and viscometry. The FTIR results confirmed the presence of functional groups of the FAME produced during transesterification. The results showed that transesterification can proceed much faster under microwave irradiation than when using traditional heating methods. The interaction between the alcohol and oil molecules is significantly improved, leading to shorter reaction times (seconds instead of hours) and improved diesel yields. The highest biodiesel yield obtained was 98% at 1:6 oil-to-methanol molar ratio for both 1 wt% and 1.5 wt% potassium hydroxide (KOH) at a reduced reaction time (30 seconds). The chemical composition of FAME (biodiesel) obtained from different conditions i contained palmitic acid (C16:0), stearic acid (C18:0), oleic acid (C18:1) and 70% linoleic acid (C18:2). The physical properties (cetane number, viscosity, density and FAME content) of biodiesel produced met the SANS 1935 specification. The energy consumption was reduced from 1.2 kWh with the traditional transesterification to 0.0067 kWh with the microwave transesterification. Microwave irradiation was shown to be effective in significantly lowering the energy consumption for production of biodiesel with good quality for small scale producers. / Thesis (MSc (Engineering Sciences in Chemical Engineering))--North-West University, Potchefstroom Campus, 2013

Many innovations have been attempted to shorten drying time or improve dehydration techniques for foods. Despite the recent advances in science and technology the bulk of dried fruit production throughout the world, over 1 1/2 billion tons (dry basis), is prepared by the energy of the sun (Copley and Van Arsdel, 1964), However, other techniques and processes for food dehydration and preservation are occupying more prominent positions in the overall production of dehydrated foods, particularly in the more advanced countries. Economics notwithstanding, it is readily apparent that dehydration as compared to sun-drying offers at least two main advantages. It is more sanitary and it is independent of inclement weather and thus of geographies. These two reasons arc perhaps among the chief ones for the increasing technical developments in dehydration by procedures such as cabinet drying (Beavens, 1944), vacuum drying (Schroeder and Schwarz, 1949), freeze drying (Lawler, 1963) and foam-mat drying (Morgan and Ginnette, 1960). They are perhaps also the reason for continuing research on new and improved dehydration processes which may be adaptable to certain types of products. In this continuing search, electromagnetic waves, which are similar to the more familiar light or radiowaves but differ in frequency and wavelength, have received little attention.

Malaria is an infectious disease caused by various forms of the Plasmodium parasite. It is responsible for thousands of deaths yearly with 90 % of those deaths being in sub-Saharan Africa, thus making it a disease of global importance. The global burden of malaria is worsened by resistance to current treatment, a lack in funding and limited research outputs. More alternative ways of treatment must be explored and may include the co-formulation of antimalarial drug substances as well as alternative ways of drug delivery. Antifolates are drugs which interfere with an organism’s folate metabolism by inhibiting dihydropteroate synthase (DHPS) or dihydrofolate reductase (DHFR). Dapsone is a synthetic sulfone which has a mechanism of action that is very similar to that of sulphonamides. The mechanism of action is characterised by the inhibition of folic acid synthesis through the inhibition of dihydropteroate synthase (DHPS). Another antifolate drug, proguanil, is the prodrug of cycloguanil. Its mechanism involves the inhibition of dihydrofolate reductase (DHFR), thus inhibiting the malaria parasite to metabolise folates and therefore stunting its growth. Unfortunately, dapsone has a serious side-effect in people with a deficiency of the enzyme glucose-6-phosphate dehydrogenase (G6PD) causing oxidative stress on the red blood cells leading to the rupturing of these cells. The main objective of this study was to formulate and characterise TMC-TPP microparticles loaded with the effective but toxic drug combination of dapsone and proguanil and to determine if these drug-containing microparticles had in vivo efficacy against malaria. N-trimethyl chitosan chloride (TMC), a partially quaternised chitosan derivative, shows good water solubility across a wide pH range thus having mucoadhesive properties and excellent absorption enhancing effects even at neutral pH. A faster, more efficient microwave irradiation method was developed as an alternative to the conventional synthesising method of TMC. TMC with the same degree of quaternisation (DQ), ± 60 %, was obtained in a quarter of the reaction time (30 min) by using the newly developed method. The TMC synthesised with the microwave irradiation method also exhibited less degradation of the polymer structure, thus limiting the chance for the formation of any unwanted by-products (Omethylation, N,N-dimethylation and N-monomethylation). The formation of complexes by ionotropic gelation between TMC and oppositely charged macromolecules, such as tripolyphosphate (TPP), has been utilised to prepare microparticles which are a suitable drug delivery system for the dapsone-proguanil combination. Both these drugs were successfully entrapped. These particles were characterised and the in vivo efficacy against the malaria parasites was determined. The microparticles with both the drugs, separately and in combination, displayed similar or better in vivo efficacy when compared to the drugs without the TMC microparticles. An in vitro dissolution study was also performed by subjecting the dapsone and proguanil TMC formulations to 0.1N HCl dissolution medium. Samples were withdrawn after predetermined time points and the drug concentration was determined with HPLC. It was found that the TMC microparticles resulted in a sustained release profile since only 73.00 ± 1.70 % (dapsone) and 55.00 ± 1.90 % (proguanil) was released after 150 minutes. The in vivo bioavailability of the dapsone and proguanil TMC formulations was evaluated in mice by collecting blood samples at predetermined time points and analysing the samples with a sensitive and accurate LC-MS/MS method. The in vivo bioavailability of the dapsone TMC formulation relative to the normal dapsone formulation was found to be 244 % and 123 % for the proguanil TMC formulation relative to the normal proguanil formulation. These TMC-TPP microparticles formulations showed better in vivo efficacy and bioavailability when compared to the normal formulation. Together with the sustained release, these formulations may be a promising cheaper and more effective treatment against malaria. / PhD (Pharmaceutics), North-West University, Potchefstroom Campus, 2015

Malaria is an infectious disease caused by various forms of the Plasmodium parasite. It is responsible for thousands of deaths yearly with 90 % of those deaths being in sub-Saharan Africa, thus making it a disease of global importance. The global burden of malaria is worsened by resistance to current treatment, a lack in funding and limited research outputs. More alternative ways of treatment must be explored and may include the co-formulation of antimalarial drug substances as well as alternative ways of drug delivery. Antifolates are drugs which interfere with an organism’s folate metabolism by inhibiting dihydropteroate synthase (DHPS) or dihydrofolate reductase (DHFR). Dapsone is a synthetic sulfone which has a mechanism of action that is very similar to that of sulphonamides. The mechanism of action is characterised by the inhibition of folic acid synthesis through the inhibition of dihydropteroate synthase (DHPS). Another antifolate drug, proguanil, is the prodrug of cycloguanil. Its mechanism involves the inhibition of dihydrofolate reductase (DHFR), thus inhibiting the malaria parasite to metabolise folates and therefore stunting its growth. Unfortunately, dapsone has a serious side-effect in people with a deficiency of the enzyme glucose-6-phosphate dehydrogenase (G6PD) causing oxidative stress on the red blood cells leading to the rupturing of these cells. The main objective of this study was to formulate and characterise TMC-TPP microparticles loaded with the effective but toxic drug combination of dapsone and proguanil and to determine if these drug-containing microparticles had in vivo efficacy against malaria. N-trimethyl chitosan chloride (TMC), a partially quaternised chitosan derivative, shows good water solubility across a wide pH range thus having mucoadhesive properties and excellent absorption enhancing effects even at neutral pH. A faster, more efficient microwave irradiation method was developed as an alternative to the conventional synthesising method of TMC. TMC with the same degree of quaternisation (DQ), ± 60 %, was obtained in a quarter of the reaction time (30 min) by using the newly developed method. The TMC synthesised with the microwave irradiation method also exhibited less degradation of the polymer structure, thus limiting the chance for the formation of any unwanted by-products (Omethylation, N,N-dimethylation and N-monomethylation). The formation of complexes by ionotropic gelation between TMC and oppositely charged macromolecules, such as tripolyphosphate (TPP), has been utilised to prepare microparticles which are a suitable drug delivery system for the dapsone-proguanil combination. Both these drugs were successfully entrapped. These particles were characterised and the in vivo efficacy against the malaria parasites was determined. The microparticles with both the drugs, separately and in combination, displayed similar or better in vivo efficacy when compared to the drugs without the TMC microparticles. An in vitro dissolution study was also performed by subjecting the dapsone and proguanil TMC formulations to 0.1N HCl dissolution medium. Samples were withdrawn after predetermined time points and the drug concentration was determined with HPLC. It was found that the TMC microparticles resulted in a sustained release profile since only 73.00 ± 1.70 % (dapsone) and 55.00 ± 1.90 % (proguanil) was released after 150 minutes. The in vivo bioavailability of the dapsone and proguanil TMC formulations was evaluated in mice by collecting blood samples at predetermined time points and analysing the samples with a sensitive and accurate LC-MS/MS method. The in vivo bioavailability of the dapsone TMC formulation relative to the normal dapsone formulation was found to be 244 % and 123 % for the proguanil TMC formulation relative to the normal proguanil formulation. These TMC-TPP microparticles formulations showed better in vivo efficacy and bioavailability when compared to the normal formulation. Together with the sustained release, these formulations may be a promising cheaper and more effective treatment against malaria. / PhD (Pharmaceutics), North-West University, Potchefstroom Campus, 2015

The solid acid catalyst of the Keggin-type 12-tungstophosphoric acid (H3PW12O40, HPW) is supported on partially reduced graphene oxide (PRGO) nanosheets for acid-catalyzed reactions. HPW is a new class of catalyst with a good thermal stability and high Bronsted acidity in order to replace common mineral acids. However, it has low specific surface area (1-5 m2/g). Therefore, the possibility of PRGO as a catalytic support for HPW is investigated due to its high surface area (2630 m2/g) and good thermal stability. The synthesis of HPW-GO catalyst is prepared using microwave and laser irradiation without using any chemical reducing agents. The HPW-GO catalysts are characterized by Ultraviolet-visible spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FT-IR), Raman Spectroscopy, X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD) techniques, and Transmission Electron Microscopy (TEM). Also, the surface acidity is measured by a non-aqueous titration of n-butyl amine. Furthermore, the application for catalysts is tested by three acid-catalyzed reactions: Esterification, Friedel-Crafts acylation, and Pechmann condensation. The greatest acidity for the microwave irradiation method is with the loading of 85 wt% HPW-GO and 60wt% HPW-GO for laser irradiation. The results observed provide an excellent opportunity for PRGO as a catalytic support for HPW for acid-catalyzed reactions.

Zinc Oxide (ZnO) is one of the most extensively studied semiconductors because of its unique properties, namely, its wide band gap (3.37 eV) and high excitation binding energy (60 meV). These properties make ZnO a promising material for uses in a broad range of applications including sensors, catalysis and optoelectronic devices. The presented research covers a broad spectrum of these interesting nanomaterials, from their synthesis and characterization to their use as photocatalyts. A new synthetic approach for producing morphology controlled ZnO nanostructures was developed using microwave irradiation (MWI). The rapid decomposition of zinc acetate in the presence of a mixture of oleic acid (OAC) and oleylamine (OAM) results in the formation of hexagonal ZnO nanopyramids and ZnO rods of varying aspect ratios. The factors that influence the morphology of these ZnO nanostructures were investigated. Using ligand exchange, the ZnO nanostructures can be dispersed in aqueous medium, thus allowing their use as photocatalysts for the degradation of malachite green dye in water. Photocatalytic activity is studied as a function of morphology; and, the ZnO nanorods show enhanced photocatalytic activity for the degradation of the dye compared to hexagonal ZnO nanopyramids. After demonstrating the catalytic activity of these ZnO nanostructures, various ways to enhance photocatalytic activity were studied by modification of this MWI method. Photocatalytic activity is enhanced through band gap modulation and the reduction of electron-hole recombination. Several approaches were studied, which included the incorporation of Au nanoparticles, N-doping of ZnO, supporting ZnO nanostructures on reduced graphene oxide (RGO), and supporting N-doped ZnO on N-doped RGO. ZnO-based nanostructures were studied systematically through the entire process from synthesis and characterization to their use as photocatalysis. This allows for a thorough understanding of the parameters that impact these processes and their unique photocatalytic properties.

Proton exchange membrane fuel cells are one of the most promising hydrogen energy conversion devices for portable, mobile and stationary applications. For wide spread usage to produce electricity platinum loading has to be decreased by using highly active electrocatalysts. Even 10 ppm carbon monoxide or higher than 30% carbon dioxide cause performance losses via deactivation which can be diminished by using binary catalysts. The aim of this thesis is to develop new platinum based electrocatalysts with high catalytic activity and to overcome the problems due to the deactivation. platinum and platinum-ruthenium based catalysts on different carbon supports have been prepared by supercritical carbon dioxide deposition and microwave irradiation methods. By using supercritical carbon dioxide deposition platinum on Vulcan XC72R (VXR), multi wall carbon nanotube (MWCNT) and Black Pearl 2000 (BP2000) catalysts were prepared and characterized by XRD, TEM and cyclic voltammetry (CV). XRD results showed that in catalysts prepared by using supercritical carbon dioxide deposition method, the particle sizes as low as 1-2 nm can be obtained. From the CV results the electrochemical surface areas obtained were Platinum/VXR&gt / Platinum/MWCNT&gt / PlatinumBP2000. By means of the oxygen reduction reaction (ORR), the number of electrons transferred per oxygen molecule was calculated as 3.5, 3.6 and 3.7 for Platinum/BP2000, Platinum/VXR and Platinum/MWCNT, respectively. The microwave irradiation was used to prepare platinum on VX, Regal and BP2000 and platinum-ruthenium on VX. The effects of microwave duration, base concentration, carbon support used and surfactant/precursor ratios were investigated. The particle sizes of the catalysts were ranging between 2-6 nm. The prepared catalysts were characterized by XRD, XPS, and then PEMFC tests were performed. The performance was ordered as Platinum/VX&gt / Platinum/Regal&gt / Platinum/BP2000. The power losses arising from carbon dioxide in hydrogen feed were decreased by using prepared platinum-ruthenium based catalysts.