The birth of nanotechnology era has revolutionized materials science, catalysis and field of optoelectronics. Novel and unique phenomena emerge when material dimensions are reduced to ultra-small size regime and enter nanometre (2-100 nm) realm. Such novel materials are expected to replace bulk materials, offering lower cost of manufacturing and enabling progress in many areas such as solar cell, drug delivery, quantum communication and computing, catalysis and sensing applications. With the progress in nanomaterial synthesis and fabrication, the need for the state-of-art characterization techniques became obvious; such techniques help to establish a complete understanding of the nature and interactions of nanosized materials. In this thesis, the first part focuses on the synthesis of gold and ruthenium clusters, namely Au8, Au9, Au101, Ru3, Ru4 and AuRu3, using the well-established synthetic protocols in the literature. Apart from the standard lab-based characterization techniques such as nuclear magnetic resonance (NMR), UV-visible spectroscopy (UV-vis) and Fourier Transform Infra-red (FTIR), a less explored but useful technique far infra-red (far IR) spectroscopy, available at the Australian Synchrotron (AS), was employed to investigate the vibrational modes in these clusters. Peaks in the experimental far IR spectra were assigned unambiguously to specific vibrations by comparing with the ones generated via DFT calculations with the help of collaborators, group of Professor Gregory Metha, University of Adelaide. For the Au9 cluster, three significant gold core vibrations are observed at 157, 177 and 197 cm-1 in the experimental spectrum. In the case of the Ru3 cluster, only a single ruthenium core vibration is identified within the spectrum, at 150 cm-1 with the calculated force constant, k = 0.33 mdyne/Å. The Ru4 cluster exhibits two metal core vibrations at 153 and 170 cm-1 with force constants of 0.35 and 0.53 mdyne/Å, respectively. Substitution with a gold atom yielding a mixed metal AuRu3 cluster shifts the core transitions toward higher wavenumbers at 177 and 299 cm-1 with an increase in force constants to 0.37 and 1.65 mdyne/Å, respectively. This is attributed to the change in chemical composition and geometry of the metal cluster core. A combination of the DFT calculations and high quality synchrotron-based experimental measurements allowed the full assignment of the key transitions in these clusters. Next, these clusters were fabricated into heterogeneous catalysts by depositing on different metal oxide nanopowders. Synchrotron X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) studies were performed at the Australian Synchrotron and the Photon Factory synchrotron in Japan to investigate the electronic structure of Au8, Au9 and Au101 on TiO2 catalysts. The XPS analysis reveals that “as-deposited” Au8 and Au9 retain some un-aggregated clusters while Au101 show bulk-like gold. These findings are in line with TEM observations, where the aggregates (large particles, > 2 nm) of Au8, Au9 and Au101 are hardly seen under HRTEM. UV-visible diffuse reflectance spectroscopy (UV-vis DRS) studies show the absence of localised surface plasmon resonance (LSPR) peaks in these “as-deposited” clusters, suggesting they are below 2 nm in size. Importantly, the XAS spectrum of “as-deposited” Au9 clusters estimates that 60% of pure, un-aggregated Au9 clusters and 40% of bulk gold in the sample. Upon calcination under O2 and combined O2 and H2 (O2-H2), Au8, Au9 and Au101 clusters form larger nanoparticles (> 2 nm) with the appearance of LSPE peak in UV-vis DR spectra. In addition, majority of the phosphine ligands (that stabilise the gold core) dislodge and form phosphine oxide-like species by interacting with oxygen on the TiO2 surface. The third part focused on testing the catalytic performance of the supported Au8, Au9, Au101, Ru3, Ru4 and AuRu3 clusters on different TiO2, SiO2, ZnO and ZrO2 in benzyl alcohol oxidation. Au101-based catalysts display the highest catalytic activity with a turn-over frequency (TOF) up to 0.69 s-1. The high catalytic activity is attributed to the formation of large Au nanoparticles (> 2 nm) that coincides with the partial removal of capping ligands. Au8 and Au9 clusters which contain NO3- counter anions are found to be inactive in benzyl alcohol oxidation. Further work shows that the presence of NO3- species diminishes the catalytic activity. Monometallic ruthenium clusters, Ru3 and Ru4, are found to be inactive yet the bimetallic AuRu3 clusters are active in benzyl alcohol oxidation, suggesting the synergistic effect between ruthenium and gold metal. Investigation of catalytic testing parameters reveals that tuning selectivity of the product is possible through manipulating the reaction temperature. Finally, a joint experiment with Prof. Wojtek Wlodarski’s group at RMIT, Melbourne was undertaken to test the sensing ability of Au9 clusters for hydrogen detection. Au9 clusters were deposited onto radio-frequency (RF) sputtered WO3 films at two different concentrations; 0.01(S1) and 0.1(S2) mg/mL. It was found that the optimal temperatures for sensor S1 and S2 were 300 °C and 350 °C, respectively. The sensor with lower Au9 concentration (S1) displays a faster response and recovery time, and a higher sensitivity toward H2. HRTEM studies reveal that the sensor S1 contain a significant population of sub-5 nm Au nanoparticles which might be responsible for a faster rate of H2 adsorption and dissociation. The key finding in this study suggest that the addition of catalytic layer such as ultra-small Au9 clusters results in improved sensitivity and dynamic performance (response and recovery time) of H2 sensors. In summary, this thesis demonstrated that cluster-based nanomaterials have wide range of applications spanning from catalysis to sensing. Further improvements in material synthesis and use of multiple complimentary characterization techniques allowed better understanding of the nature of the key active species (metal nanoparticles) assisting design of catalysts and sensors with enhanced performance.

We plan to study the attachment of a cationic tetranuclear palladium II-based macrocyclic square onto a planar gold surface or a gold nanoparticle. To understand the possible mechanisms of attachment of inorganic molecular square to gold we will see if certain related salts can cause an induced aggregation of nanoparticles.The replacement of the surface-passivated citrate layer on the gold nanoparticles can be characterized by infrared spectroscopy and shifts in the surface plasmon resonance band. Consequently, if it can bond gold nanoparticles via electrostatic interactions, then it may be possible that the square can attach to a planar gold surface by a similar mechanism.Infrared spectra of the aggregated nanoparticles will be compared to those obtained using the attachment of molecular square on a planar gold surface. By comparing.infrared spectra it may be possible to determine by what mechanism the square is attaching to gold. / Department of Chemistry

Discussions and considerations around nationalisation of the mining sector in South became more prevalent from 2009. There are certain implications or consequences related to these discussions, considerations or decisions that should be taken into account. The purpose of this study will be to determine what these consequences may be in a South African context by making inference from historic cases of nationalisation in other countries as well as testing the perceptions of respondents from a gold mine. In order to achieve the purpose of this study the researcher will do an in-depth literature study on the concept, history, consequences and related aspects of nationalisation. The perceived consequences will be tested by doing an empirical study on a sample of a gold mine. An online questionnaire has been distributed to the selected sample. The results have been collected by the researcher and was analysed by the Statistical Consultation Services at the North-West University (Potchefstroom Campus). Conclusions have been drawn from the analysed data and are reflected in the document. The results from the empirical study confirmed in most cases what the literature study has identified. The conclusions and recommendations have been provided by the researcher after taking into account the results of the literature and empirical study. / Thesis (MBA)--North-West University, Potchefstroom Campus, 2013

Discussions and considerations around nationalisation of the mining sector in South became more prevalent from 2009. There are certain implications or consequences related to these discussions, considerations or decisions that should be taken into account. The purpose of this study will be to determine what these consequences may be in a South African context by making inference from historic cases of nationalisation in other countries as well as testing the perceptions of respondents from a gold mine. In order to achieve the purpose of this study the researcher will do an in-depth literature study on the concept, history, consequences and related aspects of nationalisation. The perceived consequences will be tested by doing an empirical study on a sample of a gold mine. An online questionnaire has been distributed to the selected sample. The results have been collected by the researcher and was analysed by the Statistical Consultation Services at the North-West University (Potchefstroom Campus). Conclusions have been drawn from the analysed data and are reflected in the document. The results from the empirical study confirmed in most cases what the literature study has identified. The conclusions and recommendations have been provided by the researcher after taking into account the results of the literature and empirical study. / Thesis (MBA)--North-West University, Potchefstroom Campus, 2013

This thesis is a dissertation to support the development of new domino pericyclic oxy-Cope/ene/Claisen/Diels-Alder reaction, diversity oriented synthesis of PPAPs scaffold via sequential one pot cascade reaction and ethyl aluminum sesquichloride catalyzed highly hindered Diels-Alder reaction. The first part concentrates on the domino pericyclic oxy-Cope/ene/Claisen/Diels-Alder reaction. As a result of this study, we have developed a general methodology for rapidly constructing complex diterpenes and discovered a thermal oxy-Cope/ene/Claisen/Claisen rearrangement, applied to the synthesis of trans decalin benzofurans. The second part involved the development of an efficient synthetic approach towards bicyclo[3.3.1]nonenone core found in many natural products, via a sequential Diels-Alder/gold(I)-catalyzed 6-endo-dig cyclization and its application to the synthesis of a diversified library of PPAPs. Finally, we have developed an efficient synthetic methodology for the formation of cyclohexene rings bearing quaternary carbon centers via an ethyl aluminum sesquichloride mediated highly hindered Diels-Alder reaction. This method solved an important problem encountered in the synthesis of many natural products including PPAPs. This methodology opened new opportunities in the total synthesis of PPAPs.

<p>The importance of nitrogen-containing compounds in human life has drawn us to focus on the preparation of amine derivatives, combined with the limitations associated with traditional methods for the formation of C-N bonds has prompted us to develop new and efficient syntheses, of amine and ether derivatives and explore the mechanisms of the gold(I)-catalyzed reactions.</p><p>A mixture of AuCl[P(t-Bu)2o-biphenyl] (5 mol %) and AgOTf (5 mol %) served as an effective catalyst for the intermolecular hydroamination of allenes with arylamines to form N-prenylaniline and N,N-diprenylaniline derivatives. This gold(I)-catalyzed protocol was effective for the formation of arylamines at non-forcing conditions with wide substrate scope in both allene and aniline, in high yields with good regioselectivity diastereoselectivity.</p><p>The mechanism of the gold(I)-catalyzed hydroalkoxylation and hydroamination of alcohols and carbamates with allenes, catalyzed by AuIPrCl (IPr= 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) and AgOTf was investigated. The experimental rate laws for both reactions indicate first-order behavior in nucleophile and catalyst and zero-order behavior in catalyst. We propose an outer-sphere mechanism with turnover limiting protonolysis for the gold(I)-catalyzed hydrofunctionalization of allenes with alcohols or carbamates based on kinetic isotope effect, saturation behavior, and stereochemical analysis of hydroalkoxylation.</p><p>The mechanism of gold(I)-catalyzed hydroamination of allenes with arylamines was examined. Specifically, we explored the hydroamination of 3-methy-1,2-butadiene with aniline catalyzed by AuCl[P(t-Bu)2o-biphenyl] (5 mol %) and AgOTf (5 mol %) in dioxane at 45 °C to form N-prenylaniline and N,N-diprenylaniline. The kinetics of this reaction were determined to be first-order in aniline, allene, and catalyst. We have concluded that the mechanism for the gold(I)-catalyzed intermolecular hydroamination of allenes with arylamines involves outer-sphere attack of aniline on the gold-&#61552;-allene complex based on stereochemical analysis of the hydroamination product from the reaction of an enantiomerically enriched allene, (R)-1-phenyl-1,2-butadiene, with 3-bromoaniline.</p> / Dissertation

No description available.

Gold nanoparticles exhibit an array of properties, both intrinsic (chemical) and extrinsic (photothermal), that can be exploited for their use in cancer therapeutics. Owing to their size and ease with which they can be functionalized with various ligands, gold nanoparticles represent a class of highly functional biomedically relevant nanostructures. Here, we explore the use of gold nanoparticles as intrinsic (chemical) antineoplastic agents, with their ability to cause DNA damage and cytokinesis arrest, to induce apoptosis in a metallic composition-dependent manner, as well as their ability to enhance sensitivity to chemotherapy by regulation of the cell cycle. The extrinsic (photothermal) properties of gold nanoparticles are also examined, in detail, through both theoretical and experimental assessment, for their use as photothermal contrast agents in vitro. Based on this assessment, the gold nanoparticles are tested in the plasmonic photothermal therapy of head and neck cancer in a mouse model.

No description available.

The development of an open pit mine at the Endeavour 42 (E42) epithermal gold deposit, situated in the Junee-Narromine Volcanic Belt of the Ordovician Macquarie Arc, central New South Wales, has provided a 3D view of the structurally controlled deposit which was hitherto not available due to the paucity of outcrop in the region. Outcropping geological relationships present a complicated history of overprinting structural deformation and vein events, including the spatial characterization of the gold-mineralizing system. Host rocks consisting of interbedded sedimentary and resedimented volcaniclastic facies, trachyandesite and porphyritic andesite lavas and intrusions (coherent and autoclastic facies), intruded by a large diorite sill, were initially tilted and faulted, followed by the emplacement of multiple dyke phases along faults. Economic gold mineralization at E42 is restricted to faults, fault-hosted breccias, and veins, and was deposited over a period spanning two distinct structural regimes. Early gold-bearing veins are steeply dipping and interpreted as forming coevally along two sets of faults and dykes within a tensional stress regime. High grade fault-hosted, hydrothermally cemented breccia intervals are included temporally with early gold-bearing veins based on comparable mineralogy and steep, fault parallel orientations. Crosscutting the early steep gold-bearing vein sets are two populations of coeval inclined gold-bearing veins, dipping moderately to the southwest and northwest, respectively, which formed in a compressional stress regime with tension directed subvertically. The E42 epithermal deposit likely developed in the period of overall crustal extension, ca. 443-433 Ma, following Phase 1 of the Late Ordovician – Early Silurian Benambran Orogeny. The generation of permeability, styles of fracture propagation, and the reactivation of pre-existing planes of weakness in the rock package are key factors in the development and current geometry of the E42 gold deposit. High grade veins and faults are commonly flanked by sericite-quartz ± carbonate alteration haloes, which exhibit consistent geochemical patterns for metals and pathfinder elements, both laterally away from structures, and vertically within the deposit. Au, Ag, As, Hg, Sb, Tl, Cu, Pb, and Zn, all display increasing concentrations towards high-grade structures, as well as higher up in the epithermal system, with varying dispersion haloes.