Theoretical waste minimisation opportunities and options for electroplating were sought from the literature. Their suitability under the specific site conditions of a chromium electroplating plant were evaluated using the results of a waste minimisation audit (audit). The audit showed that many waste minimisation practices were already in place. These included counter current flowing rinse systems, multiple use of rinses and recycling of the drag-out solution back into the plating solution. Two types of information were collected during the audit, namely new chemical monitoring (concentration levels of sodium, iron, zinc, copper, lead, chromium and nickel and conductivity, total dissolved solids and pH) and flow rate data and existing data (composition of the process solutions, products and waste outputs, and raw materials, workpieces and utility inputs). The data were analysed using four established waste minimisation techniques. The Scoping Audit and the Water Economy Assessment results were determined using empirically derived models while the Mass Balancing and the True Cost of Waste results were obtained through more detailed calculations. The results of the audit showed that the three most important areas for waste minimisation were water usage, effluent from rinse water waste streams and nickel consumption. Water usage has the highest waste minimisation potential followed by nickel. Dragged-out process chemicals and rinse water consumption contribute to ranking the effluent stream the most important waste minimisation opportunity identified by the True Cost of Waste Analysis. Potential financial savings were roughly estimated to be in the order of R 19949 and R 126603 for water and nickel respectively. Intervention using only "low cost-no-cost" waste minimisation measures was recommended as a first step before contemplating further focus areas or technical or economical feasibility. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2004.

Commercial sunscreen products are used to protect the skin against hannful ultraviolet (UV) radiation that can induce skin cancer at high dosage. These products contain UV filters that can reflect, scatter or absorb UV light. The chemical UV filters responsible for the absorption of UV radiation can be photochemically modified and as a result reduce the efficacy of the sunscreen formulation. This study focused on the possible use ofplant polyphenols as potential stabilisers of photo-unstable sunscreen chemical absorbers. The photo-instability of some sunscreen absorbers results in radical formation; this prompted the use of the plant, Sutherlandia microphylla (Cancer Bush plant), as a potential photostabiliser. The Cancer Bush plant is used by the indigenous people of South Africa to treat AIDS and cancer. The radical scavenging properties of polyphenolic compounds present in the plant are possibly responsible for the plant's anti-tumour and anti-IDV properties. Therefore, these Cancer Bush polyphenols could possibly be used to photostabilise photo-unstable sunscreen absorbers. Potential polyphenolic photostabilisers from the Cancer Bush plant were extracted by means of various polyphenolic extraction methods. These extracts were analysed by gas chromatography (GC), high-performance liquid chromatography (HPLC), UV spectroscopy and gas chromatography-mass spectrometry (GC-MS). The phenolic content and the antioxidant activity ofthese extracts were investigated by means of the Folin-eiocalteu reagent (FCR) and the diphenylpicrylhydrazyl (DPPH) radical assays respectively. Polyphenols were also extracted from various Rooibos teas and compared with those extracted from the Cancer Bush plant. Both the Cancer Bush and various Rooibos tea extracts were found to contain simple phen~lics and potential polyphenolic compounds. The Cancer Bush extracts as well as the Rooibos tea extracts together with the specific polyphenols, epicatechin and rutin, were assessed for their ability to photostabilise sunscreen absorbers. The photostability of the chemical absorbers in the absence and in the presence of the polyphenol extracts was investigated by UV spectroscopy, by monitoring their absorption spectra during irradiation with solar-simulated radiation. These extracts inhibited the photodegradation of the absorber avobenzone. The photostability of avobenzone is solventIntroduction III dependent hence the investigations were carried out in three solvents, namely, cyclohexane, ethyl acetate and dimethylsulfoxide. Additionally, the cause ofthe instability ofavobenzone in these solvents was investigated by means of DV spectroscopy, HPLC and nuclear magnetic resonance spectroscopy. The oxygen dependency of the photo-instability of avobenzone was also determined. The photo-instability of avobenzone was found to occur as a result of photoisomerisation and!or photodegradation, depending on the solvent. Avobenzone photoisomerised extensively in dimethylsulfoxide and photodegraded appreciably in cyclohexane, whereas both processes occurred to a similar extent in ethyl acetate. Photoisomerisation only occurred in the presence of oxygen whereas photodegradation occurred irrespective of oxygen. The Cancer Bush and various Rooibos tea extracts as well as other polyphenols photostabilised avobenzone in ethyl acetate and dimethylsulfoxide but not in cyclohexane. This photostabilisation effect was potentially due to the radical scavenging ability of polyphenols which prevented the oxygendependent photoisomerisation, but not the oxygen independent photodegradation process from occurring. / Thesis (M.Sc.)-Chemistry-University of KwaZulu-Natal, 2005

The use of supported catalysts to essentially combine the positive traits offered by both homogeneous and heterogeneous catalysis has become a competitive field of research. In particular, hydrotalcite-like catalysts (HTIc) has proven to be valuable for this purpose. Various osmium - containing catalysts were synthesized according to the co-precipitation method viz. Os-Cu-HTIc, Os-Ni-HTlc and the Os-Co-HTlc. Techniques such as SEM, IR, EDS, XRD, ICP, BET and XPS were exploited during catalyst characterisation and these essentially confirm that the hydrotalcite (HT) structure has been obtained. Various olefin substrates, ranging from simple straight-chained alkenes to cyclic, allylic and halogenated olefins, were tested. The results are promising and suggest that the diols are produced both with high selectivity and in good yield. Further experiments suggest: 1) Ofthe various co-oxidants tested, N-methylmorpholine-N-oxide is most suitable 2) The reaction proceeds faster at 60 °C than at room temperature 3) The addition of water to the reaction mixture increases the rate of the reaction for most substrates and 4) The catalyst is thermally stable and produces better results when calcined at 200 0 C prior to use This thesis reports that a new heterogeneous catalytic system for the efficient and selective cisdihydroxylation of olefins has been developed - one which suggests no leaching of metal into the reaction solution and no over-oxidation products. / Thesis (M.Sc.)-University of KwaZulu Natal, 2004.

A chromium plating line used by a local company was monitored to identify any potential waste minimisation opportunities. Plating of the workpiece surface is carried out by immersing the workpiece in seven process (treatment) solutions including nickel and chromium plating baths. Between each process step the workpieces are rinsed. The chromium plating process was evaluated using the results of a waste minimisation audit. This involved gathering data on the composition, flow rates and costs of the inputs of the process. Two types of data were collected namely new and existing data. The new data included chemical monitoring (concentration levels of Ni, Cr, Na, S, B, P, Si, Fe, Cu, Zn, Pb as well as conductivity, TDS, SS and pH measurements) and water usage data. The existing data included raw materials, utility inputs, composition of process solutions and product outputs. The data were analysed using three established waste minimisation techniques. The Water Economy Assessment (a form of Monitoring and Targeting) results were determined using an empirically derived model. The Water Balance and True Cost of Waste results were obtained through more detailed calculations using the results of the chemical analysis. The results from the audit showed that the water usage on the chromium plating line has the highest waste minimisation potential. The True Cost of Waste analysis showed there is no significant chemical wastage in the effluent stream. The potential savings of the effluent stream was negligible (approximately R10 for 238 days). Drag-out calculations were also performed and showed that the drag-out volumes were in good agreement with the typical volumes found in the metal finishing industry. Intervention using simple lowcost and no-cost waste minimisation opportunities were recommended as a first step before contemplating further focus areas for technical or feasibility studies. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2009.

This study involved an assessment of the Pietermaritzburg Waste Minimisation Club (PWMC) during 2001, and a waste minimisation audit conducted at two coil coating lines. Waste minimisation is the reduction or elimination of waste at source4 • It is often achieved through waste minimisation clubs which comprise a small number of companies, generally in the same geographicaI area, that are interested in reducing waste 1"711 . The success of the PMWC was evaluated in terms of the degree to which members implemented waste minimisation principles. Two questionnaires were used to assess the success of the club. These indicated that although the training material gave the members a good understanding of the basic principles of waste minimisation, the material has not given the members enough practical information to implement a waste minimisation programme in their companies. The main barriers to waste minimisation identified include production pressure, operational constraints, lack of human resources and a lack of management time. The drivers for waste minimisation were financial savings, improved plant utilisation and improved environmental performance. Coil coating is a continuous process where a coiled sheet of aluminium is cleaned, pretreated and coated with paint. The flow rates, compositions and costs of all input and output streams to the cleaning and pretreatment sections were gathered from operators or measured. The data were collected over a three-month period to obtain a representative sample, and then analysed to determine waste minimisation opportunities using mass balances, monitoring and targeting, a scoping audit and a true cost of waste assessment. The scoping audit was found to be the most useful technique because it accurately prioritised the waste minimisation opportunities but required a relatively small amount of data for its application. However, the scoping audit underestimated the savings that could be achieved at the coil coating department and therefore the 'scope to save' percentages, which were developed for United Kingdom industries, need modification to better reflect South African industry. Opportunities for waste minimisation on Coil Coating Line 1 (CCL1) included reducing the water consumption, reducing the acid and chromium raw materials consumption, and finding a cheaper energy source for heating the process and rinse tanks. Potential fmancial savings of R116 000 and environmental savings of 18 200 kL of water or effluent per year were calculated for CCL1. The chromium and acid effluent treatment and solid waste disposal are the main areas for waste minimisation on Coil Coating Line 2 (CCL2). Savings could be achieved in these areas by using roller application ofthe chromium pretreatment rather than spray application, and by preventing a leak of chromium pretreatment into the acid process and rinse tanks. Other savings can also be achieved by operating the chromium process tank as a fed-batch process, and operating the alkali and acid process tanks as continuous processes at the specified chemical concentrations and with recycle of the rinse water (dragout). The total financial savings that can be achieved on CCL2 are R5.3 million, and potential environmental savings are 31 600 kL ofeffluent per year. / Thesis (M.Sc.)- University of Natal, Pietermaritzburg, 2002.

The topical application of sunscreens is widely practised to protect healthy and photosensitive skins from the sun. The benzophenone-derived sunscreens, e.g. 2-hydroxy-4-methoxy benzophenone-5-sulphonic acid (or benzophenone-4) and 2-hydroxy-4-methoxy benzophenone (or benzophenone-3), were ranked as the second and third most frequently used sunscreens, respectively, by the United States Food and Drug Administration (FDA) in 1996. These sunscreens are categorised as being 'safe' and 'effective'. However, it is well known that the parent compound, benzophenone, undergoes rapid hydrogen abstraction reactions on irradiation and is an extremely powerful radical generator. In addition, benzophenone has been shown to be a potent photosensitizer of thymine dimers in deoxyribose nucleic acid (DNA). More astounding to the sunscreen industry is the recent discovery that a group of non-steroidal anti- inflammatory drugs (NSAIDs) having the benzophenone backbone, e.g. ketoprofen, not only form thymine dimers when irradiated with DNA in vitro, but also photosensitize double stranded supercoiled DNA making it prone to single-strand break formation. Both these lesions, if unrepaired, may contribute to mutagenesis, carcinogenesis, inherited disease and eventually cell death. The purpose of this investigation was to determine if a group of benzophenone-derived sunscreen agents has the ability to photosensitize the cleavage of DNA, whereby supercoiled DNA is converted to the relaxed circular and linear forms. The group of UV absorbers investigated in this study included benzophenone-4, benzophenone-3 , 2,4 dihydroxybenzophenone (or benzophenone-l), 2,2'-dihydroxy-4,4'-dimethoxy benzophenone sulphonic acid (or trade name Uvinul DS49) and 2-phenylbenzimidazole-5-sulphonic acid (or trade name Eusolex 232). For comparison the parent compound benzophenone and the NSAID ketoprofen, a well-known photocleaver, were also studied. Buffered aqueous solutions of the benzophenones were irradiated in the presence of DNA at wavelengths greater than 300 nm with an Osram 500 W/2 high-pressure mercury lamp in conjunction with a 10 mm thick Pyrex filter. The irradiated samples were analysed for DNA cleavage by agarose gel electrophoresis and for DNA binding by fluorescence spectroscopy. The photostability of the UV absorbers was also investigated. In addition, computational studies were conducted to obtain the lowest energy geometrical structures of these UV absorbers and hence determine if intercalation of these UV absorbers with DNA was possible. From the photostability experiments conducted, it is apparent that the benzophenone-based UV absorbers were stable to photodecomposition when irradiated with UV light. They behaved in a manner different from their parent compound benzophenone, and from ketoprofen, where substantial photodegradation occurred upon UV irradiation. This is indicative of the rapid photoreactivity of the benzophenone backbone. The relative photostability of the UV absorbers was not anticipated and was attributed to the substituents present on the benzophenone backbone. The agarose gel electrophoresis experiments however clearly showed that benzophenone, ketoprofen, benzophenone-l, Uvinul DS49 and Eusolex 232 cleave ?X174 DNA when irradiated with UV light at wavelengths greater than 300 nm, while benzophenone-3 and benzophenone-4 did not. For these UV absorbers with the exception of benzophenone-3 and benzophenone-4, the number of single strand breaks in the DNA increased compared to when it was irradiated in their absence. In addition, the supercoiled DNA was converted to the relaxed circular and linear forms, the latter of which was undetected in the absence of the UV absorbers. Binding of benzophenone, ketoprofen, benzophenone-l and Uvinul DS49 to calf thymus DNA was also detected by the fluorescence spectroscopy technique. However, this was not observed for Eusolex 232, benzophenone-3 and benzophenone-4, since they did not compete with ethidium bromide for DNA binding sites. Where DNA cleavage did occur, the mechanism of this interaction had to be determined hence the motivation for the computational studies. From computational studies using PM3 semi- empirical calculations, it was determined that the benzophenone-based UV absorbers investigated, apart from Eusolex 232, displayed non-planar geometrical structures. This indicated that DNA intercalation of these sunscreen agents with DNA would at best be very limited, since only one half of the molecule could possibly interact with the bases of DNA. For benzophenone, ketoprofen, benzophenone-l and Uvinul DS49, photosensitised type I and type II processes involving triplet energy transfer reactions has been identified in literature as being responsible for DNA cleavage. It was determined by ab initio calculations that Eusolex 232 exists in a planar structure unlike the other UV absorbers mentioned above that were non- planar. It was concluded that although Eusolex 232 has the ability to intercalate with the base pairs of DNA, it does not do so, as shown by its lack of binding to calf thymus DNA by the fluorescence spectroscopy study. Literature alludes to photooxidation by singlet oxygen in single stranded DNA via the type II reaction and type I electron transfer reactions in double stranded DNA as the mechanism responsible for DNA cleavage induced by Eusolex 232. / Thesis (M.Sc.)-University of Natal, Durban, 2003.

The synthesis of p-lactams has been of foremost importance since the discovery of penicillin by Sir Alexander Fleming, in 1928, and its susequent structure elucidation in 1945. Ethyl N-2-bromo-alkylcarbamates show considerable potential as precursors to p- lactams. In the past, p-lactams have been prepared by many methods, none of which have involved 2-3 bond formation. The proposed ring closure using ethyl N-2-bromoalkylcarbamate involves 2-3 bond formation, making this method of synthesis novel. This work describes two attempted methods of cyclisation. The first using a Grignard reagent, and the second, using abstraction of an acidic proton a to a phosphonate group. These methods of intramolecular cyclisation were based on analogous intermolecular additions, which are also described. The second method was also used to determine the general potential of ethyl N-bromo- alkylcarbamtes as precursors to other heterocyclic systems. / Thesis (M.Sc.)-University of Natal, Durban, 2001. / NRF & NRF/DEA & T.

SAPPI SAICCOR is a pulp and paper mill situated in Umkomaas, 50 kms south of the port of Durban in South Africa. It was the first company to produce high grade dissolving pulp from the Eucalyptus tree and is currently the world's largest manufacturer of chemical cellulose. SAICCOR is one of the few pulp and paper mills that produces its dissolving pulp by the acid sulphite process using both calcium and magnesium as bases in the form of calcium bisulphite and magnesium bisulphite. Four streams of effluent are produced during their process, namely, the calcium spent liquor, the magnesium pulp condensate and two streams from the bleaching stages. An acid hydrolysis of the effluent streams yielded a range of organic compounds such as lignans and lignin - type precursors as well as a triterpenoid. Column chromatography and thin layer chromatography, using various ratios of hexane, dichloromethane, ethyl acetate and methanol, were carried out in isolating and purifying the compounds. The structures of these compounds were determined using NMR spectroscopic and mass spectrometric techniques. / Thesis (M.Sc.)-University of Natal, Durban, 2003.

No abstract available. / Thesis (M.Sc.)-University of Natal, Durban, 2001.

Ledebouria ovatifolia (Bak.) lessop, Clivia caulescens R.A.Dyer and Haemanthus pauculifolius Snijman & Van Wyk were the three species investigated in this work. Ledebouria ovatifolia belongs to the family Hyacinthaceae (Liliaceae sensu lato) and, to date, the chemical composition of this species has not been investigated. Members of this family are widely distributed, but are particularly well represented in Southern Africa. The Ledebouria genus was formerly classified as part of the Scilla genus from which a large number of naturally occurring oxygen heterocycles known as homoisoflavonoids have been isolated. In this work the bulbs of L. ovatifolia were investigated and two compounds were isolated. These were the homoisoflavonoid, 5,7-dihydroxy-3-(4'-hydroxybenzyl)-4-chromanone and the chalcone, 6',2'-dimethoxy-4,4'dihydroxychalcone, both of which are known naturally occurring compounds. Clivia caulescens and Haemanthus pauculifolius are both members of the Amaryllidaceae family. The plants of the Amaryllidaceae family form a large group of over sixty genera, which are concentrated mainly in Southern Africa. Plants from this family have been extensively used in traditional medicines and many have pharmacological properties. The compounds responsible for most of these effects are a group of isoquinoline alkaloids, which are found almost exclusively in plants belonging to this family. The alkaloids isolated from plants belonging to this group are known to cause poisoning in low doses and can cause excessive salivation and diarrhoea. Higher doses of the active compounds can cause CNS depression and large enough doses can prove fatal. Although many of these alkaloids are harmful to man, some of the unique Amaryllidaceae alkaloids exhibit anti-tumour and anti-viral activities, and are thus potentially beneficial to man. The Clivia genus is endemic to South Africa and the most common species, C. miniata, is used by traditional healers to facilitate childbirth and as a snake bite remedy. In this chemical investigation both the bulbs and the leaves of C. caulescens were investigated. The ethanol extract of the bulbs yielded four alkaloids, hippeastrine, haemanthamine, lycorine and ll-(S)-hydroxyvittatine. The investigation of the leaf extract also yielded lycorine and hippeastrine as well as an additional alkaloid sternbergine. Haemanthus pauculifilius is a recently described member of the Haemanthus genus, which consists of 27 taxa that are restricted to Southern Africa and Namibia. In this chemical investigation the ethanol extract of the bulbs and leaves yielded the common triterpenoid sitosterol as well as two novel 5,11-methanomorphanthridine type alkaloids, montanine hydrochloride and manthidine. / Thesis (M.Sc.)-University of Natal, Durban, 1999.