Over the last 100 Years, the cyanidation process has been the most popular method for recovering gold from its ores. Despite this, there are still efforts to improve the efficiency of the process, particularly as ores become more difficult to treat. Many investigators have studied the cyanidation process, although a large proportion of these studies have obtained contradictory results. This thesis presents a kinetic and electrochemical study of the leaching of gold in cyanide solutions, and emphasis is placed on rationalising the conflicting results which have been published in the past.The leaching rate of gold was measured using a rotating electrochemical quartz crystal microbalance, an instrument which allows the simultaneous measurement of electrochemical data and mass changes at the solid-solution interface in real time. A proportion of this project was devoted to the on-going design of this instrument, and a number of modifications are discussed in detail. Initially, the leaching of gold in cyanide solutions was investigated under conditions of high purity. Under these conditions, it was found that the gold surface is blocked by a passive film, presumably AuCN. The presence of such a film results in the reaction being chemically controlled, and under typical cyanidation conditions (4 mM cyanide, pH 10.0), the rate of dissolution is very low. These kinetic results were supported by complimentary electrochemical studies, which showed that gold is passive in the potential region where cyanidation occurs.The second part of this thesis presents a study of the effect of system purity on the leaching of gold in cyanide solutions. Solution phase purity was investigated by adding controlled amounts of lead or silver to the leach solutions. It was found that in the presence of low concentrations of lead, the dissolution of gold in 20 mM cyanide solutions was oxygen ++ / diffusion controlled (as compared to chemical control for gold in the absence of lead). However, high concentrations of lead were found to be detrimental to the leaching process. It is believed that the role of lead is to modify the surface by cementation, hence reducing the effect of the passive film. Silver was also found to be effective at reducing passivation, and the role of silver believed to be similar to that of lead. It was found that unlike lead, high concentrations of silver are not detrimental to the dissolution of gold in cyanide solutions.Solid phase purity was also found to be important in the leaching of gold, and it was found that the leaching of a gold sample which contains 1 % silver is diffusion controlled. This finding is important from an industrial viewpoint, as most native gold contains some silver. Consequently, attempts were made to rationalise the leaching of gold/silver with current plant practice. Discussion on the effect of cyanide and oxygen concentrations, temperature and lead addition is presented.

Solid-phase syntheses of two 14-membered ring peptidomimetics were done to determine whether or not a beta-turn structure can facilitate macrocyclization. NMR methods, together with CD and QMD calculations, do not fully support this assumption. However, cyclizations of more ordered structures like those of compounds 2 were more efficient than those for highly strained ring systems like 1. A small library of 18-membered ring peptidomimetics that accommodate an extra amino acid residue was synthesized on resin. Their syntheses were not complicated by head-to-tail dimer impurity, unlike those for previously synthesized 14-membered systems. These larger macrocycles exhibit beta-turn structures as verified by NMR, CD and QMD techniques. Moreover, two compounds in this series (3a and 3g) were shown to have agonistic properties for TrkC in cell survival assays. Dimerization of monovalent mimics was achieved first by modifying the organic template so that monovalent mimics with requisite functional groups can be synthesized. Second, the monovalent units were dimerized using sequential nucleophilic substitutions on fluorescently labeled dichlorotriazine. Our rationale to make bivalent compounds out of monovalent ones was justified when compound 4 was shown to bind TrkA with a 20 nM affinity. Reactions of amino acids with NH4SCN under acylating conditions produced 2-thiohydantoins in which the nitrogen of the amino acid (N1) was acylated. This was proven by 2-D NMR which showed no cross-peak between the NH signal observed and the Cα±-H of the amino acid. When the compound was deacylated, a new NH signal appeared and the corresponding cross-peak with the Cα±-H was observed. Solution-phase syntheses of non-peptidic mimics were achieved by doing a double substitution on a dihalogenated nitrobenzene scaffold. Sonogashira and SNAr reactions were done to install the required side-chains to give the desired compounds. These non-peptidic compounds can be easily adapted to our DTAF-Inp dimerization protocol since the nitro groups can be easily reduced. Attempts to make a spirotetracyclic peptidomimetic with three side chain mimics were done by synthesizing the spirocyclic diketopiperazine precursor. The synthesis of the DKP was achieved by making the cyclic quaternary amino acid that was coupled to another amino acid via the HOAt-EDC method. This protocol gave dipeptides in high yields. These dipeptides were deprotected and cyclized to the DKP under mildly acidic conditions in toluene.

Solid-phase syntheses of two 14-membered ring peptidomimetics were done to determine whether or not a beta-turn structure can facilitate macrocyclization. NMR methods, together with CD and QMD calculations, do not fully support this assumption. However, cyclizations of more ordered structures like those of compounds 2 were more efficient than those for highly strained ring systems like 1. A small library of 18-membered ring peptidomimetics that accommodate an extra amino acid residue was synthesized on resin. Their syntheses were not complicated by head-to-tail dimer impurity, unlike those for previously synthesized 14-membered systems. These larger macrocycles exhibit beta-turn structures as verified by NMR, CD and QMD techniques. Moreover, two compounds in this series (3a and 3g) were shown to have agonistic properties for TrkC in cell survival assays. Dimerization of monovalent mimics was achieved first by modifying the organic template so that monovalent mimics with requisite functional groups can be synthesized. Second, the monovalent units were dimerized using sequential nucleophilic substitutions on fluorescently labeled dichlorotriazine. Our rationale to make bivalent compounds out of monovalent ones was justified when compound 4 was shown to bind TrkA with a 20 nM affinity. Reactions of amino acids with NH4SCN under acylating conditions produced 2-thiohydantoins in which the nitrogen of the amino acid (N1) was acylated. This was proven by 2-D NMR which showed no cross-peak between the NH signal observed and the Cα±-H of the amino acid. When the compound was deacylated, a new NH signal appeared and the corresponding cross-peak with the Cα±-H was observed. Solution-phase syntheses of non-peptidic mimics were achieved by doing a double substitution on a dihalogenated nitrobenzene scaffold. Sonogashira and SNAr reactions were done to install the required side-chains to give the desired compounds. These non-peptidic compounds can be easily adapted to our DTAF-Inp dimerization protocol since the nitro groups can be easily reduced. Attempts to make a spirotetracyclic peptidomimetic with three side chain mimics were done by synthesizing the spirocyclic diketopiperazine precursor. The synthesis of the DKP was achieved by making the cyclic quaternary amino acid that was coupled to another amino acid via the HOAt-EDC method. This protocol gave dipeptides in high yields. These dipeptides were deprotected and cyclized to the DKP under mildly acidic conditions in toluene.

Metal chalcogenide nanomaterials are interesting due to their size dependent properties and potential use in numerous types of devices or applications. The synthetic methods of binary phase metal chalcogenide nanoparticles are well established, but finding simple ways to make even more complex nanostructures is important. To this end, two techniques were studied: the cation exchange of metal chalcogenide nanocrystals, CdE → MxEy (E = S, Se, Te; M = Pd, Pt) and the solution phase synthesis of ternary chalcogenide nanoparticles. The effects of cation solvation and the volume change (Delta V) of reaction on the equilibrium and the morphology change in the cation-exchange reactions of CdE → MxEy were investigated. A two-phase solvent environment was particularly efficient in increasing the thermodynamic driving force. The effect of Delta V of reaction on the morphology of the product nanocrystals was also investigated. Depending on the stress developed in the lattice during the reaction, product nanocrystals underwent varying degrees of morphological changes, such as void formation and fragmentation, in addition to the preservation of the original morphology of the reactant nanocrystals. The knowledge of the effect of ion solvation and Delta V of reaction on the equilibrium and product morphology provides a new strategy and useful guide to the application of cation-exchange reactions for the synthesis of a broader range of inorganic nanocrystals. Using a solution phase method, the morphology of CuInSe2 nanoparticles could be tuned from small 10 nm spheres to micron length nanowires by varying the relative amount of strong and weak surfactants passivating the surface. Oleylamine and trioctylphosphine oxide were chosen as the strong and weak surfactants, respectively. Small isotropic structures were formed when the oleylamine was the only surfactant with the size of the nanospheres increasing as the amount of oleylamine decreased. For the CuInSe2 nanowires, weakly-binding dioctylphosphine oxide (DOPO), an impurity in the TOPO, was found to be the key surfactant that enables the anisotropic one-dimensional growth. Detailed analysis of the structure of the nanowires indicated that they grow perpendicular to (112) planes, with twinning around the growth axis by ~60 degree rotation. The nanowires exhibit a saw-tooth surface morphology resembling a stack of truncated tetrahedral.

abstract: The use of nanoparticle-in-matrix composites is a common motif among a broad range of nanoscience applications and is of particular interest to the thermal sciences community. To explore this morphological theme, crystalline inorganic composites were synthesized by mixing colloidal CdSe nanocrystals and In2Se3 metal chalcogenide complex (MCC) precursor in hydrazine solvent and then thermally transform the MCC precursor into a crystalline In2Se3 matrix. The volume fraction of CdSe nanocrystals was varied from 0 to ~100% .Rich structural and chemical interactions between the CdSe nanocrystals and the In2Se3 matrix were observed. The average thermal conductivities of the 100% In2Se3 and ~100% CdSe composites are 0.32 and 0.53 W/m-K, respectively, which are remarkably low for inorganic crystalline materials. With the exception of the ~100% CdSe samples, the thermal conductivities of these nanocomposites are insensitive to CdSe volume fraction.This insensitivity is attributed to competing effects rise from structural morphology changes during composite formation. Next, thermoelectric properties of metal chalcogenide thin films deposited from precursors using thiol-amine solvent mixtures were first reported. Cu2-xSeyS1-y and Ag-doped Cu2-xSeyS1-y thin films were synthesized, and the interrelationship between structure, composition, and room temperature thermoelectric properties was studied. The precursor annealing temperature affects the metal:chalcogen ratio, and leads to charge carrier concentration changes that affect Seebeck coefficient and electrical conductivity. Incorporating Ag into the Cu2-xSeyS1-y film leads to appreciable improvements in thermoelectric performance. Overall, the room temperature thermoelectric properties of these solution-processed materials are comparable to measurements on Cu2-xSe alloys made via conventional thermoelectric material processing methods. Finally, a new route to make soluble metal chalcogenide precursors by reacting organic dichalcogenides with metal in different solvents was reported. By this method, SnSe, PbSe, SnTe and PbSexTe1-x precursors were successfully synthesized, and phase-pure and impurity-free metal chalcogenides were recovered after precursor decomposition. Compared to the hydrazine and diamine-dithiol route, the new approach uses safe solvent, and avoids introducing unwanted sulfur into the precursor. SnSe and PbSexTe1-x thin films, both of which are interesting thermoelectric materials, were also successfully made by solution deposition. The thermoelectric property measurements on those thin films show a great potential for future improvements. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

The objective of this Ph.D. study is to explore an important and fertile research topic on the methods for synthesis of nanomaterials by homogeneous nonaqueous solution phase reaction. Research in this work focuses on synthesizing several kinds of nanomaterials in different environments and structure, including spherical nanoparticles, nanowires and core-shell structure composites We first synthesized metallic nanomaterials in this system, such as ~10 nm Fe nanoparticles, ~6 nm Au nanoparticles, and ~100 nm Bi nanoparticles, this system are the preparation for the following studies. Secondly, we synthesized bimetallic nanomaterials in this system, such as Fe50Co50 alloy and Bi doped with Mn. For FeCo alloy, after annealing at 500 °C, a pure phase of Fe50Co50 was obtained. And we first synthesized the nanowires of bismuth doped with manganese. By studying intermediates at different temperatures during the growth process of nanowires, the evolution of the crystallization of metallic products and the mechanism of the formation of the nanowires are investigated. Thirdly, we synthesized core-shell structure nanocomposites, including either gold as the shell or polymer as the shell. Au-coated magnetic Fe nanoparticles have been successfully synthesized by partial replacement reaction in a polar aprotic solvent with about 11 nm core of Fe and about 2.5 nm shell of Au. HRTEM images show clear core-shell structure with different crystal lattices from Fe and Au. SQUID magnetometry reveals that particle magnetic properties are not significantly affected by the overlayer of a moderately thick Au shell. The Aucoated particles exhibit a surface plasmon resonance peak that red-shifts from 520 to 680 nm. And Poly (Vinyl Pyrolidone) (PVP) coated iron nanoparticles also have been successfully synthesized in a polar aprotic solvent, which shows the welldefined core-shell structures. In this approach, Poly (Vinyl Pyrolidone) (PVP) was employed as the coating polymer directly coated on metallic core (iron) nanoparticles. In this work, a combination of TEM (transmission electron microscopy), EDS (Energy disperse X-ray spectroscopy), XRD (X-ray powder diffractometry), ICP (inductively-coupled plasma spectrometer), TGA (Thermogravimetric analysis), UV-visible absorption spectroscopy, IR (infrared) spectroscopy and SQUID magnetometry (Superconducting Quantum Interference Device) were employed to characterize the morphology, structure, composition and magnetic properties of the products. In summary, this Ph.D. study successfully and systematically synthesized several kinds of nanocomposites in a system. The synthetic procedure is simple, economic and easily scaled-up for further applications. And many techniques were employed to characterize the products.

The protein-protein interactions (PPIs) occur when two or more proteins are bound together. Also, this protein-protein interactions (PPIs) cause the various biological processes in the body. Due to this reason, abilities of controlling or inhibiting PPIs can give us promising advantages like (1) better understanding of biological systems, (2) development of new diagnostic approaches for health or disease, and (3) establishment of novel molecular therapeutics. Many proteins adopt the secondary structures, where most of protein-protein interactions take place. -Helices and -sheets are the prevalent secondary conformations, but there are extended secondary structures such as -hairpins, -turns, 310 helix, and so on. As a result, construction of molecules mimicking these protein secondary structures is tractable target for drug design. Moreover, in drug discovery, designing peptidomimetics or non-peptidic mimetics is a popular strategy instead using peptides or truncated peptides because peptides or truncated peptides are prone to proteolysis and degraded in the body. Also, peptidomimetics and non-peptidic mimetics have not only the similar topology as peptides but also resistance to proteolysis. Due to these advantages, in this study, peptidomimetics or non-peptidic mimetics were synthesized and tested for different targets: (1) synthesis of non-peptidic -helical mimetics for p53-MDM2 inhibition, (2) solution-phase synthesis of -hairpin peptide for the inhibition of multiple myeloma cells (MM) adhesion, and (3) synthesis of -hairpin peptoid-peptide hybrids. The synthesis in all three different studies was succeeded, but they still need some improvements. For instance, non-peptidic -helical mimetics, terpyrimidyl derivatives, were synthesized successfully, but they did not show any bioactivity against p53-MDM2. Also, they have a solubility problem. Based on these results, it is necessary to improve the pharmacokinetic properties and bioactivity by changing the substituents on the rings or structures. The -hairpin peptide for the second case already showed good bioactivity against multiple myeloma (MM). For the next level of bio-study, the considerable amount of a -hairpin peptide was demanded. In order to make the substantial -hairpin peptide, the solution phase peptide synthesis was chosen instead of the solid phase peptide synthesis because of the cost-effect. Two methodology were tried for the solution-phase peptide synthesis: (1) segment ligation and (2) continuous synthesis. In the former case, the -hairpin peptide synthesis was successful, but, in the latter case, it is necessary to investigate the appropriate coupling reagents for each step. Peptoid-peptide hybrids has been one of the popular peptidomimetics in the last two decades. Also, mimicking the peptide secondary structure in peptoids has been studied extensively these days. The combination of these two factors was the goal for the third case. Because peptoid-peptide hybrids with a secondary structure can be recognizable by native proteins and resistant to proteolysis. So far, three sets of peptoid-peptide hybrids were synthesize and checked the secondary structure formation by using NMR. However, there was no indication of the secondary structure formation in the three sets of peptoid-peptide hybrids. This result suggests that it is necessary to introduce the more constrained components in peptoid-peptide hybrids. In the above three chapters, it has been tried to find the new drug candidates by synthesizing peptidomimetics or non-peptidic mimetics. Even though the synthesis was successful, some intended results such as the bioactivity or the secondary structure formation were not obtained. However, these results can give us the inspirations to improve properties of peptidomimetics or non-peptidic mimetics for a certain purpose, which leads to earn the intended results and eventually find new drug candidates.

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