Hydrogen cyanide gas (HCN{g)) is formed during the process of extracting gold from ore and may pose a risk to the health of the workers at the gold refinery (Mill/plant), especially the risk of detrimental effects on the central nervous system and the cardiovascular system. The measurement of the personal airborne HCN(g) exposure of a worker using sorbent tubes, provides the concentration of the chemical that the worker breaths in. The measurement of the urinary thiocyanate (SCN~) concentration provides the total HCN exposure experience by the worker through all possible routes of exposure. The study's aim was to determine if the workers were exposed to HCN(g) concentrations that was higher than the occupational exposure limit (OEL) , which would mean that the workers are exposed to excessive and possibly harmful levels of HCN. The monitored workers were divided into three homogenous exposure groups or HEGs, according to the their potential level of exposure. The results were compared between the three HEGs and between three work description groups, namely the Mill/plant workers, SGS laboratory assistants and members of the environmental department. The study found that all the workers were exposed to personal airborne HCN(9) concentrations below the OEL. A statistical significant difference was found the personal airborne exposure experienced by the three HEGs and between the Mill/plant workers and the members of the environmental department. No statistical significant difference was found between the urinary SCN" concentration found in the three HEGs or the between the three work description groups. Confounding factors such as smoking, the consumption of cassava, the exposure to fire smoke and the amount of time worked at the mine did not influence the urinary SCN~ concentration. The implementation of a biological monitoring program would enable the identification of any worker that is exposed to excessive levels of HCN. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2009.

<p><p>The wide-spread occurrence of biologically active nitrogen-containing heterocycles and allylic amines inspired us to develop atom-economical methods for their syntheses.</p></p><p><p>A cationic gold(I) <italic>N</italic>-heterocyclic carbene complex catalyzed the intermolecular hydroarylation of allenes with indoles to form (<italic>E</italic>)-allylic indoles in modest to good yield at room temperature. The protocol was effective for monosubstituted, 1,3-disubstituted, and tetrasubstituted allenes and various indoles.</p> </p><p><p>Platinum(II) bis(phosphine) complexes catalyzed the intermolecular hydroamination of monosubstituted allenes with secondary alkylamines in good yield with selective formation of (<italic>E</italic>)-allylic amines. The scope of the protocol included aryl and alkyl monosubstituted allenes as well as a variety of both cyclic and acyclic secondary alkylamines.</p></p><p><p>The scope of gold(I)-catalyzed intermolecular hydroamination of 1-alkenes with 1-methyl-2-imidazolidinone was expanded to include additional 1-alkenes functionalized with carboxylic acid derivatives. However, a nucleophile screen failed to identify nucleophiles other than cyclic ureas and 2-oxazolidinone that efficiently undergo hydroamination with 1-alkenes. Various carbamates, arylamines, amide derivatives, sulfur-containing amide derivatives, and &alpha;-heteroatom compounds failed to react with 1-octene under gold(I)-catalyzed conditions.</p></p><p><p>A chiral bis(gold) phosphine complex catalyzed the stereoconvergent, intermolecular enantioselective hydroamination of chiral, racemic 1,3-disubstituted allenes with carbamates to form <italic>N</italic>-allylic carbamates in good to high yield with up to 92% <italic>ee</italic>. In addition, enantiopurity experiments suggested the nature of the catalytically active species changes with increasing concentration of <italic>N</italic>-allylic carbamate.</p></p> / Dissertation

Inkjet printing of ceramic components and gold conductive tracks was carried out in this study. A commercial inkjet printer, designed for printing one layer of 2D images on paper, was modified to give adequate resolution, to reverse the substrate for overprinting many layers and to accommodate the increase in thickness of 3D components during printing. Ceramic inks were prepared by wet ball milling and printed to form 3D structures. The powders used were alumina, zirconia, lead zirconate titanate (PZT) and barium titanate. The substrate used for printing the ceramic parts was an overhead transparency. Methods to stop or reduce ink flow were devised and used during printing of the ceramic parts. The alumina and zirconia powders were used for the fabrication of multi-layered laminates. The lead zirconate titanate was used to fabricate components with pillars, walls, vertical channels and x-y-z channel network. During printing of the x-y-z channel network, carbon was used as a support structure and then removed during firing. Barium titanate and carbon powders were used to form the first storey of a capacitor with a multi-storey car park structure. The printed parts were pyrolysed and fired in an oxidising environment and then characterised with scanning electron microscopy. The causes of micro structural defects found were discussed and prevention methods suggested. Organic gold powder was dissolved in methanol and then printed on three different substrates to form conductive gold tracks. The substrates used included alumina, glazed tile and microscope glass slides. The printed tracks were fired in air. The decomposition characteristics of the organic gold compound were studied with TGA and Differential Scanning Calorimetry (DSC). Scanning electron microscope was used to examine the fired gold film for defects and conductivity measurement of the tracks was carried out with a programmable multimeter.

The objectives of this thesis were to optimize the synthesis and surface coating of metallic and semiconductor nanoparticles, to understand how these materials interact with cells and physiological systems and to investigate how they can be used to deliver thermal therapy for medical applications. Reproducible high-yield synthesis of gold nanorods and surface coating with a variety of polymers and silica was optimized. Using gold nanorods as a model system, the relationship between particle surface chemistry, surface charge and cellular uptake was studied, as well as the toxicity of nanoparticles of different surface chemistry. Low toxicity in vitro was encouraging and was confirmed in vivo by intravenously injecting Sprague-Dawley rats with semiconductor quantum dots of various surface coatings. Low toxicity was found during biochemical, haematological and pathological assessment, and these results indicate that applications of nanoparticles should be further investigated. One such application is the use of near infrared absorbing gold nanorods in remotely activated hyperthermia. It was shown that gold nanorods act synergistically with the chemotherapeutic cisplatin to improve cytotoxicity, and reduce the required cytotoxic drug dose to 33% of the unheated amount. Due to the success of hyperthermia treatment in vitro, continuing and future work involves the use of gold nanorods ex vivo on excised human corneas in a novel application to weld corneal tissue for improved wound closure following cataract surgery.

The blood brain barrier (BBB) remains a major challenge to the advancement and application of systemic anti-cancer therapeutics into the central nervous system. The structural and physiological delivery constraints of the BBB significantly limit the effectiveness of conventional chemotherapy, thereby making systemic administration a non-viable option for the vast majority of chemotherapy agents. Furthermore, the lack of specificity of conventional systemic chemotherapy when applied towards malignant brain tumors remains a major shortcoming. Hence novel therapeutic strategies that focus both on targeted and enhanced delivery across the BBB are warranted. In recent years nanoparticles (NPs) have emerged as attractive vehicles for efficient delivery of targeted anti-cancer therapeutics. In particular, gold nanoparticles (AuNPs) have gained prominence in several targeting applications involving systemic cancers. Their enhanced permeation and retention within permissive tumor microvasculature provide a selective advantage for targeting. Malignant brain tumors also exhibit transport-permissive microvasculature secondary to blood brain barrier disruption. Hence AuNPs may have potential relevance for brain tumor targeting. However, the permeation of AuNPs across the BBB has not been well characterized, and hence is a potential limitation for successful application of AuNP-based therapeutics within the central nervous system (CNS). In this dissertation, we designed and characterized AuNPs and assessed the role of polyethylene glycol (PEG) on the physical and biological properties of AuNPs. We established a size-dependent permeation profile with respect to core size as well as PEG length when AuNPs were assessed through a transport-permissive in-vitro BBB. This study was the first of its kind to systematically examine the influence of design on permeation of AuNPs through transport-permissive BBB. Given the significant delivery limitations through the non-transport permissive and intact BBB, we also assessed the role of magnetic resonance imaging (MRI) guided focused ultrasound (MRgFUS) disruption of the BBB in enhancing permeation of AuNPs across the intact BBB and tumor BBB in vivo. MRgFUS is a novel technique that can transiently increase BBB permeability thereby allowing delivery of therapeutics into the CNS. We demonstrated enhanced delivery of AuNPs with therapeutic potential into the CNS via MRgFUS. Our study was the first to establish a definitive role for MRgFUS in delivering AuNPs into the CNS. In summary, this thesis describes results from a series of research projects that have contributed to our understanding of the influence of design features on AuNP permeation through the BBB and also the potential role of MRgFUS in AuNP permeation across the BBB.

Heat shock protein 70 (HSP70) is an important health related biomarker, being implicated as an early stage cancer marker and as an indicator of cardiac health. It also has important implications in wildlife environmental monitoring, as its levels can be affected by food deprivation, elevated temperatures, and pollution. Therefore, the use of HSP70 as a biomarker is highly desirable, yet the current methods of quantifying HSP70 are time consuming, expensive, and require dedicated labs. In order to facilitate widespread use of the HSP70 biomarker, a quantification tool that can be used at the point-of-care is needed. This implies the development of a simple and inexpensive HSP70 biosensing technique that is highly sensitive and selective. Therefore, in this work a label-free HSP70 biosensor has been designed based on the optical properties of gold nanoparticles (NPs). Gold NPs exhibit a large absorbance peak in the visible spectrum due to localized surface plasmon resonance (LSPR). The peak position is dependent on the local refractive index, which can be employed as a biosensor by selectively capturing the target analyte to the NP surface. To design an LSPR HSP70 sensor, optical and fluidic simulations were developed to determine optimal NP geometries and microchannel dimensions. The results showed optimal response when using 100nmx5nm gold nanotriangles inside of a 100μmx100μm microchannel. Simulations of the sensor performance showed HSP70 detection from 0.92-4000ng/ml with a resolution of 1.1ng/ml, all of which satisfied the design requirements. An LSPR sensor was experimentally tested at the benchtop scale to prove the concept. Gold NPs were fabricated by electron beam lithography and enclosed in a polymer flow cell. For initial testing of the LSPR sensor, the NPs were functionalized with biotin for selective capture of streptavidin. Streptavidin was detected in real time over the range 55-500,000ng/ml. The use of bovine serum albumin (BSA) was shown to be necessary to block non-specific binding sites to ensure a streptavidin-specific response. The LSPR sensor was then demonstrated to detect salmon HSP70 at 4600ng/ml using its synthetic antibody. Overall, these results demonstrate that LSPR can be used to realize an HSP70 biosensor suitable for point-of-care applications.

Different types of biomass samples including fungi and algae were treated for their gold and cobalt uptake capacity. The performance of activated carbon and ion-exchange resins were compared with the metal uptake capacity of the biosorbents. Sargassum natans, a brown seaweed, exhibited a high gold uptake capacity outperforming the ion-exchange resin and equalling activated carbon. Algal biomass of Ascophyllum nodosum proved to be a very potent biosorbent for cobalt. While the temperature, agitation and biomass particle size did not affect the metal uptake process, the effect of pH was significant for both gold and cobalt uptakes. The optimum pH for gold uptake was 2.5 and for cobalt, was 4-5. The kinetics of cobalt biosorption was relatively rapid (5 min) at the initial concentration of the metal in solution, 100 mg/L. The biosorptive uptake of gold required 2 h to reach equilibrium when the initial concentration of gold was 100 mg/L. None of the tested cations, such as K$ sp+$, Ca$ sp{2+}$, Fe$ sp{2+}$, Cr$ sp{3+}$, UO$ sbsp{2}{2+}$, Ni$ sp{2+}$, Zn$ sp{2+}$, Ag$ sp+$, affected the gold uptake capacity of S. natans biomass under the optimum conditions. Anions, such as NO$ sbsp{3}{-}$, SO$ sbsp{4}{2-}$, CO$ sbsp{3}{2-}$, PO$ sbsp{4}{3-}$, and Pb$ sp{2+}$ suppressed the gold uptake somewhat. Under the optimum process conditions cations, except K$ sp+$ and Fe$ sp{2+}$, and anions, NO$ sbsp{3}{-}$ in particular, exhibited a pronounced negative effect on the cobalt uptake by A. nodosum biomass. / Sequestered gold was eluted with a mixture of thiourea and ferric ammonium sulphate solution. Approximately 98% of sequestered gold was eluted with 17 h in a batch contacting system at the optimum solids (biomass)-to-liquid ratio of 5 and pH of 5. At increased temperatures, the gold elution rate increased only slightly. Efficient desorption of cobalt was achieved using CaCl$ sb2$/HCL solution at pH 3. Cobalt elution time was quite short. Temperature affected neither desorption rate nor the equilibrium. The optimum solid-to-liquid ratio was 12 for desorption of cobalt from A. nodosum biomass. / The gold taken up by the biosorbent was deposited in its elemental form. / Available mathematical models, including the REDEQL2 chemical equilibrium model, were tested for theoretical predictions of co-ion competition in attempt to better understand the biosorption mechanism. (Abstract shortened with permission of author.)

Catalytically relevant metal clusters were deposited on metal oxide supports. Palladium and gold were deposited on mixed morphology ZnO, and palladium was deposited on MgO(100). The materials were characterized with electron microscopy, photoluminescent spectroscopy, and X-ray photoelectron spectroscopy. The behavior of hydrogen on these materials, as well as bare ZnO, was studied using volumetric isotherms. The isotherms were used to determine the monolayer gas coverage, surface area, and heats of adsorption of hydrogen on these materials over the temperature range of approximately 8-13 K. At the temperatures and pressures studied, hydrogen physically adsorbed onto the materials. Additional investigations with inelastic neutron scattering were conducted on palladium decorated ZnO and bare ZnO. These revealed that hydrogen molecules on bare ZnO act as three dimensional free rotors, but hydrogen on palladium decorated ZnO acts as a two-dimensional planar molecule and undergoes a 6.2% bond length extension.

Thesis (Ph. D.)--University of Hawaii at Manoa, 1995. / Includes bibliographical references (leaves 221-240). / Microfiche. / x, 240 leaves, bound 29 cm

The Mt. Milligan deposit is a tilted (~45°) Cu-Au alkalic porphyry located 155 km northwest of Prince George, B.C., Canada. It is the youngest of the BC alkalic porphyry deposits, all of which formed between 210 to 180 Ma in an extensive belt of K-enriched rocks related to the accretion of the Quesnellia-Stikinia superterrane to ancestral North America. Mt. Milligan has a measured and indicated resource of 205.9 million tonnes at 0.60 g/t Au and 0.25% Cu containing 3.7 million oz. gold, and 1.12 billion lb. copper. Shoshonitic volcanic and volcaniclastic andesites host mineralization. These have been intruded by a composite monzonitic stock (MBX stock), and associated sill (Rainbow Dike). Early disseminated chalcopyrite-magnetite and accessory quartz veins are associated with K-feldspar alteration in the MBX stock. A halo of biotite alteration with less extensive magnetite replaces host rocks within a ~150 m zone surrounding the stock, while K-feldpsar alteration extends along the Rainbow Dike and permeable epiclastic horizons. Peripheral albite-actinolite-epidote assemblages surround the K-silicate zone. Albite-actinolite occurs at depth, and epidote dominates laterally. Copper and Au grade are maximal where the albite-actinolite assemblage overprints biotite alteration. Gold grade is moderate in association with epidote, whereas Cu is depleted. The post-mineral Rainbow Fault separates the core Cu-rich zone from a downthrown Au-rich zone. A similar zonation of metals occurs in the hanging-wall (66 zone), where a Cu-bearing, potassically-altered trachytic horizon transitions to a funnel-shaped zone of pyrite-dolomite-sericite-chlorite alteration with elevated gold. Sulfide S-isotope compositions range from -4.79 δ34S in the central Cu-Au orebody to near-zero values at the system periphery, typical of alkalic porphyries. Sulfur isotope contours reflect the magmatic-hydrothermal fluid evolution, and indicate late-stage ingress of peripheral fluids into the Cu-Au zone. Carbonate C- and O-isotope compositions corroborate the magmatic fluid path from the Cu-Au rich zone to Au-rich zone with decreasing depth. Strontium isotopic compositions of peripheral alteration minerals indicate a laterally increasing meteoric fluid component. Changes in major- and trace element composition of epidote and pyrite across the deposit are also systematic. These provide additional vectors to ore, and confirm the kinematics of the Rainbow Fault.