Inaug.diss.--Dorpat.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1976. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

The present study involves the preparation of novel mixed-ligand platinum(II) complexes in the hope of expanding the range of platinum(II) complexes that exhibit anticancer activity and which are less toxic and have a broader spectrum of activity than cisplatin and its analogues. To this end, N-(3-R-benzoyl)-N’,N’-diethylthiourea, N-(3-R-benzoyl)-N’-morpholinothiourea, N-(3-Rbenzoyl)-N’,N’-di(2-hydroxyethyl)thiourea (R = NO2, Cl, H, CH3, OCH3), N,N-diethyl-N’-menthyloxycarbonylthiourea and N-menthyloxycarbonyl-N’-morpholinothiourea ligands, and their corresponding mixed-ligand platinum(II) complexes of the type [PtCl(L)(RR’SO)], were synthesised and characterised by elemental analyses, IR, 1H and 195Pt NMR spectroscopy and, in some cases, X-ray crystallography. Dimethylsulfoxide complexes were prepared using all the ligands, while complexes containing unsymmetrically substituted sulfoxides were prepared using the N-benzoyl-N’,N’-diethylthiourea and ,N-diethyl-’-(-)-(3R)-menthyloxycarbonylthiourea ligands only. The molecular structures of cis-(S,S)-[PtCl(DMSO)(L)] (where L = N-benzoyl-N’,N’-diethylthioureato, N-(+)-(3S)-menthyloxycarbonyl-N’-morpholinothioureato), cis-(S,S)-[Pt(N-benzoyl-N’,N’-diethylthioureato)Cl(MPSO)] and cis-[Pt(N-benzoyl-N’,N’-diethylthioureato)2] were determined by X-ray crystallography. The X-ray crystal structure of N,N-diethyl-N’- (-)-(3R)-menthyloxycarbonylthiourea was also determined. The spectroscopic and crystallographic data are consistent with complexes containing a (S,O)-chelated ligand and a sulfur-bonded sulfoxide ligand. However, the 1H and 195Pt NMR studies showed that the alkoxycarbonylthioureato complexes exist as geometric isomers with the sulfoxide coordinated either in a cis-(S,S) or trans-(S,S) arrangement with respect to the sulfur donor atom of the chelated ligand, whereas the acylthioureato complexes yielded only cis-(S,S)-[PtCl(L)(RR’SO)] complexes. The difference in the coordination chemistry of the acylthiourea and alkoxycarbonylthiourea ligands was examined further by treatment of the [PtCl(DMSO)(L)] complexes, where L = Nbenzoyl-N’,N’-diethylthioureato, N-benzoyl-N’-morpholinothioureato, N,N-diethyl-N’-(-)-(3R)- menthyloxycarbonylthioureato and N-(+)-(3S)-menthyloxycarbonyl-N’-morpholinothioureato, with PPh3 to give the corresponding [PtCl(L)(PPh3)] and [Pt(L)(PPh3)2]+ complexes. 31P NMR studies of these complexes reveal that the alkoxycarbonylthioureato ligands bind less strongly than the acylthioureato ligands, which is consistent with the crystallographic studies. The morpholine derivatives of the acylthioureato and alkoxycarbonylthioureato ligand systems also appear to bind less tightly than the diethyl derivatives. The weaker binding properties of the alkoxycarbonylthioureato ligands might be a possible explanation for the observed geometric isomerisation of these complexes, with the mechanism of isomerisation involving a chelate ringiv opening step. Furthermore, crystallographic and 31P NMR studies suggest that the acylthioureato carbonyl oxygen donor atom is relatively softer and therefore has a greater trans-influence than the carbonyl oxygen donor atom of the alkoxycarbonylthioureato ligand. The substitution kinetics of the chloride and sulfoxide leaving groups by azide, iodide, thiocyanate, triphenylphosphine, 2-mercaptobenzimidazole, 4-(dimethylamino)pyridine and thiourea, from selected cis-(S,S)-[PtCl(N,N-dialkyl-N’-(3-R-benzoyl)thioureato)(RR’SO)] complexes, in methanol, were evaluated to determine if variation of the electronic properties of the chelated ligand and variation of the sulfoxide have a significant influence on the reactivity of these complexes. Two consecutive reactions were observed. It was found that neutral nucleophiles initially substitute the dimethylsulfoxide, while anionic nucleophiles substituted the chloride ligand. For all the nucleophiles studied, the first substitution step was evaluated, except for triphenylphosphine and 4-(dimethylamino)pyridine, where the second step was also evaluated. The overall order of reactivity for the first substitution step was; N3 - < DMAP < I- < SCN- < MBI < thiourea < PPh3, with the rate varying three orders of magnitude. The substitution of the dimethylsulfoxide ligand by PPh3 from cis-(S,S)-[Pt(N-benzoyl-N’,N’-diethylthioureato)Cl-(DMSO)] to form cis-(S,P)-[Pt(N-benzoyl-N’,N’-diethylthioureato)Cl(PPh3)] was confirmed by X-ray crystallography. In general, manipulation of the chelating moiety, as well as interchanging the sulfoxide did not alter the reactivity of these complexes to a great extent. The anticancer activity of all the platinum(II) sulfoxide complexes were evaluated against a HeLa cell line, of which three complexes, cis-(S,S)-[PtCl(DMSO)(N,N-diethyl-N’-(3-nitrobenzoyl)- thioureato)], cis-(S,S)-[PtCl(DMSO)(N-morpholino-N’-(3-nitrorobenzoyl)thioureato)] and cis-(S,S)-[PtCl(DMSO)(N-(3-methoxybenzoyl)-N’-morpholinothioureato)] exhibited a concentration dependent anti-proliferative effect, but were less potent than cisplatin. These three complexes displayed a similar dose response in a MCF-7 cell line. Preliminary morphology studies with the three biologically active complexes in a HeLa cell line suggest that they induce cell death by apoptosis. Preliminary pBR322 plasmid DNA binding studies of selected [Pt(acylthioureato)Cl(RR’SO)]complexes clearly indicate that these complexes have a different mode of binding to DNA than cisplatin.

The dissolution of platinum from platinum iron alloys in oxygenated hydrochloric acid/sodium chloride solutions has been investigated using an autoclave technique. The dissolution rate was found to be dependent on alloy composition, acid concentration, and oxygen pressure. The dissolution followed typical corrosion kinetics and analysis of the results indicated that the cathodic reduction of oxygen was the rate controlling step in the dissolution reaction, at high chloride ion concentrations. An apparent activation energy of 16.8 kcal per mold was found for the dissolution of PtFe alloys, and 19 kcal per mole for pure Pt sheet. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

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Thesis (MSc)--Stellenbosch University, 2013. / Please refer to full text to view abstract.

A research report submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfilment of the requirements for the degree of Masters of Science in Mining Engineering 2016/10/5 / Management does not have an efficient mechanism to test strategic and operational alternatives and to assess the impact of these on the value and underlying trade-off variables of the business. Techno-economic models can be applied for this purpose as they provide a framework for undertaking advanced process simulation and business valuation. The purpose of the research report is to identify key components, principles and best practice as applied in techno-economic models, to improve techno-economic modelling for the purpose of decision-making and business optimization. The integrated techno-economic model requires a mining model with production planning and scheduling abilities. The half-level system method can be applied to create production profiles for different mining options and only after optimisation the best option is taken forward for graphical design and detailed scheduling. A metallurgical model incorporates the logic and efficiencies of the treatment process into the techno-economic model from which the refined products are determined for revenue and costing purposes. The financial model integrates with the mining and metallurgical elements and uses detailed costing models and sound financial principles for operating and capital cost estimates. An accurate techno-economic model includes key cash flow components and applies rigorous valuation practice for investment analysis. Techno-economic models are extensively applied in business planning, major project valuations and stay–in-business project valuations. Learnings from the review of these case studies suggest best practice, which allows the models to be applied to different types of business entities and contributes to the accuracy, consistency and efficiency of techno-economic modelling. Integrated techno-economic modelling is also applicable in strategic planning and mine design optimization as it provides a powerful instrument for decision-making and business optimization. The future of the mining business depends on it as an invaluable direction steering tool. / MT2017

The platinum market is best understood through a comprehensive analysis of supply and demand. Supply is most significantly affected by production constraints and the erratic draw-down in Russian stockpiles. Total world supply of platinum for 1998 amounted to 5.915 Moz, 64% of which was produced from the Bushveld Complex in South Africa. The remainder emanated from Russia, Zimbabwe, the United States, Canada and the recycling of autocatalysts. Supply is forecast to drop by 320 000 oz in 1999 due to a lower Russian export quota and reduced Zimbabwean production. Demand for platinum is unusual, in that it is sought after both as a store of wealth, and has properties that make it irreplaceable in a host of industrial applications. Current world demand for the metal is driven by a growing Eastern jewelry market and increased use in autocatalysts due to vehicle emissions legislation. Total world demand for 1998 amounted to 5.755 Moz. A predicted steady growth in the consumption of platinum for jewelry and existing applications, together with development of new uses, is expected to result in an annual 250 000 oz increase in demand for 1999 and 2000. The derived supply and demand balance for 1998 shows a small excess in supply relative to demand. This will be absorbed by inventories and is likely to have little affect on price, A significant shortfall of 410 000 oz, however, is predicted for 1999. This is likely to be followed by a further shortfall in 2000 and will drive up prices, impel consumers towards substitution and thriving and encourage producers to expand.

Thesis (Ph.D.)--Bowling Green State University, 2009. / Document formatted into pages; contains xv, 200 p. : ill. Includes bibliographical references.

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