Thesis (Ph. D.)--Oregon State University, 2010. / Printout. Includes bibliographical references (leaves 114-125). Also available on the World Wide Web.

Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 175-188).

Thesis (Ph. D.)--University of Texas at Austin, 1998. / Vita. Includes bibliographical references (leaves 181-192). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--University of Chicago, Department of Chemistry, December 2000. / Includes bibliographical references (p. 140-150). Also available on the Internet.

In this research, the use of gold nanostructures (AuNS) was explored to evaluate the interaction between molecules and the nanoparticle (NP) surface. In that way, three different projects were developed; one project using fluorescence and two projects using Raman spectroscopy as measuring technique. The fluorescence spectroscopy project used the fluorescence lifetime imaging microscope (FLIM) to evaluate the relative position of the molecules methylene blue (MB) and cucurbit[7]uril (CB) on the gold nanoparticle (AuNP) surface. Although the inclusion complex is favored in solution, it was found that MB forms an exclusion complex with CB, when CB is attached to the AuNP surface. The first project utilizing Raman spectroscopy, specifically surface enhanced Raman scattering (SERS), took advantage of a confined system (a reverse micelle) to evaluate the Raman signal of water molecules in close proximity to the AuNP surface. It was observed that the SERS water signal had a big shift to higher energies compared with the Raman signal of the bulk water; indicating the water molecules in the system are subjected to different bond-stretching energies. The second Raman project studied the modification of two different AuNS (specifically AuNP and gold nanorod -AuNR) with thiols. Different thiols were used to evaluate the kinetics of the modification of the AuNS surface, also the different AuNS presented different ligands on their surface. In general, and considering the difference in the bonding strength of the ligands present on the AuNS surface (by synthesis) and the size of the thiol, at least 2 h are required to modify the complete AuNS surface.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2016. / The Bushveld igneous complex in northern South Africa has the largest deposit of platinum group elements (PGE) in the world. In trace amounts, these are closely associated with base metal sulphides (BMS). Froth flotation is used to beneficiate these PGE ores. The process constitutes a bulk sulphide recovery. Improvement of recovery of the BMS is required to maximise the recovery of PGEs. The performance of the froth flotation process is largely dependent on the chemical additives used and these chemicals have been extensively studied. Mixtures of collectors are widely used in the flotation of sulphide and platinum group mineral (PGM) ores. A range of performance benefits for the use of mixtures over pure collectors have been observed on many systems. These include improved valuable metal grades and recoveries, lower reagent dosage requirements, improved rates of flotation and enhanced recovery of coarse particles. Improvements observed with mixtures of chemical reagent have been attributed to synergism; defined as the interaction of two or more agents to produce a combined effect greater than the sum of their individual effects. Synergism is highly desired in froth flotation. For this study, mixtures of thiol collectors were used in batch froth flotation tests in an attempt to identify synergism between the different collectors on flotation performance of a typical platinum ore from the Merensky reef. Flotation performance was evaluated in terms of grades and recoveries of copper and nickel, and the rate of metal flotation. Single thiol collectors of xanthate (SIBX), a dithiocarbamate (DTC) and a dithiophosphate (DTP) were evaluated to determine the effect of functional group on flotation performance. SIBX was then used in mixtures with both DTC and DTP at various molar ratios to establish whether synergism occurs between these collectors on this particular platinum ore. Molar ratios of 90:10, 80:20, 70:30 60:40 and 50:50 were considered with SIBX being the major component. Further tests were conducted with the addition of a carboxymethyl cellulose depressant to the collector mixtures.

M.Sc. / The main objective of this project was to synthesize carbohydrates that contain a thiol functional group, commonly known as thiocarbohydrates and subsequently employ them as stabilizing agents in the synthesis of gold nanoparticles and as ligands in the synthesis of phosphine thiocarbohydrate gold(I) complexes. In achieving our objective, thiocarbohydrate compounds 62, 64, 69 and 71 were successfully synthesized from acetylated 60 or benzylated glucal 66 using a Ferrier rearrangement reaction. NaHSO4-SiO2 was used as a catalyst for Ferrier rearrangement reaction in the presence of dithiol type nucleophiles (i.e. 1,2-dithiol ethane or 1,5-dithiol pentane) to afford the desired thiocarbohydrate compounds. The S-acetate derivatives 63, 65, 70 and 72 of the corresponding thiocarbohydrates were prepared as a confirmatory test for the presence of the terminal thiol (SH) in the thiocarbohydrate compounds. C-2 modified thiocarbohydrate compounds 78 and 80 were synthesized from C-2 iodomethyl glycoside 77 following a literature reported procedure in the presence of 1,2-dithiol ethane or 1,5-dithiol pentane as nucleophiles. S-acetate derivatives 79 and 81 of the corresponding thiocarbohydrate compounds were synthesized again to confirm the presence of the terminal thiol (SH). All the thiocarbohydrate compounds and their corresponding S-acetate derivatives were characterized with NMR spectroscopy and HRMS. Ethyl thiocarbohydrate compounds 62, 69 and 78 were successfully employed as stabilizing agents in the preparation of gold nanoparticles GNP1-GNP9 following a Brust-Schiffrin procedure. UV-Vis spectroscopy and transmission electron microscopy (TEM) were used to characterize these gold nanoparticles. Phosphine thiocarbohydrate gold(I) complexes 84-94 were synthesized from selected thiocarbohydrate compounds. NMR spectroscopy and HRMS were used to characterize these gold(I) complexes. Having synthesized the target thiocarbohydrate compounds, gold nanoparticles and gold(I) complexes, our aim was to investigate their biological activity against cancer and HIV. However, the biological testing process took considerably longer and as a result this dissertation was submitted without the biological tests results.

M.Sc. (Chemistry) / Inhibition of mycothiol biosynthesis pathway has attracted attention from chemists and biochemists who aim to develop novel anti-TB drugs. A possible route to inhibit the production of mycothiol in cells may be via the inhibition of enzymes involved in the biosynthetic pathways. Molecular analogues that mimic mycothiol and containing tetrahedral-forming functional groups have been reported to show activity against mycothiol biosynthesis by inhibiting the enzymes in the mycothiol biosynthetic pathway...

Most pharmaceutically relevant proteins and many extracellular proteins contain disulfide bonds. Formation of the correct disulfide bonds is essential for stability in almost all cases. Disulfide containing proteins can be rapidly and inexpensively overexpressed in bacteria. However, the overexpressed proteins usually form aggregates inside the bacteria, called inclusion bodies, which contains inactive and non-native protein. To obtain native protein, inclusion bodies need to be isolated and resolubilized, and then the resulting protein refolded in vitro. In vitro protein folding is aided by the addition of a redox buffer, which is composed of a small molecule disulfide and/or a small molecule thiol. The most commonly used redox buffer contains reduced and oxidized glutathione. Recently, aliphatic dithiols and aromatic monothiols have been employed as redox buffers. Aliphatic dithiols improved the yield of native protein as compared to the aliphatic thiol, glutathione. Dithiols mimic the in vivo protein folding catalyst, protein disulfide isomerase, which has two thiols per active site. Furthermore, aromatic monothiols increased the folding rate and yield of lysozyme and RNase A relative to glutathione. By combining the beneficial properties of aliphatic dithiols and aromatic monothiols, aromatic dithiols were designed and were expected to increase in vitro protein folding rates and yields. Aromatic monothiols (1-4) and their corresponding disulfides (5-8), two series of ortho- and para-substituted ethylene glycol dithiols (9-15), and a series of aromatic quaternary ammonium salt dithiols (16-17) were synthesized on a multigram scale. Monothiols and disulfides (1-8) were utilized to fold lysozyme and bovine pancreatic trypsin inhibitor. Dithiols (11-17) were tested for their ability to fold lysozyme. At pH 7.0 and pH 8.0, and high protein concentration (1 mg/mL), aromatic dithiols (16, 17) and a monothiol (3) significantly enhanced the in vitro folding rate and yield of lysozyme relative to the aliphatic thiol, glutathione. Additionally, aromatic dithiols (16, 17) significantly enhance the folding yield as compared to the corresponding aromatic monothiol (3). Thus, the folding rate and yield enhancements achieved in in vitro protein folding at high protein concentration will decrease the volume of renaturation solution required for large scale processes and consequently reduce processing time and cost.

The oxidation of thiols in petroleum is a subject of ongoing research, discussion and removal of sulfur is a topic of ongoing legislation. The Merox® process requires high pressures and temperatures. Novel catalysts and methods innovations are of interest. This work examines the synthesis, purification and use of sodium cobalt(II) tetrasulfophthalocyanine to oxidize ethanethiol to diethyl disulfide. Many systems using phthalocyanines carry out the oxidation reaction under basic conditions. This work oxidized ethanethiol to diethyl disulfide in dimethylformamide using cobalt tetrasulfophthalocyanine (CoTSPc) under alkali free conditions and was compared to cobalt sulfate heptahydrate, cobalt phthalocyanine (CoPc), FeTSPc and CuTSPc. The reaction was carried out in oxygen saturated DMF while stirring at 15, 25 and 40.00 °C. The amount of ethanethiol remaining over time was determined using Ellman's reagent. A simple GC method quantified the amount of diethyl disulfide. The reaction proceeded to completion within 10 min at 40.00 °C. A turn over number of 72 and frequency of 8.1 min−1 is obtained. The activation energy was approximately 32 kJ/mol. The prepared CoTSPc catalyst was most catalytic toward oxidation of ethanethiol followed by cobalt sulfate heptahydrate, CoPc, FeTSPc and CuTSPc was non-catalytic.