Low Gold Concentrations Research Articles

Feasibility of spectral CT imaging for the detection of liver lesions with gold-based contrast agents – A simulation study

PurposeTo demonstrate the feasibility of gold-specific spectral CT imaging for the detection of liver lesions in humans at low concentrations of gold as targeted contrast agent. MethodsA Monte Carlo simulation study of spectral CT imaging with a photon-counting and energy-resolving detector (with 6 energy bins) was performed in a realistic phantom of the human abdomen. The detector energy thresholds were optimized for the detection of gold. The simulation results were reconstructed with the K-edge imaging algorithm; the reconstructed gold-specific images were filtered and evaluated with respect to signal-to-noise ratio and contrast-to-noise ratio (CNR). ResultsThe simulations demonstrate the feasibility of spectral CT with CNRs of the specific gold signal between 2.7 and 4.8 after bilateral filtering. Using the optimized bin thresholds increases the CNRs of the lesions by up to 23% compared to bin thresholds described in former studies. ConclusionsGold is a promising new CT contrast agent for spectral CT in humans; minimum tissue mass fractions of 0.2 wt% of gold are required for sufficient image contrast.

In Vivo Anticancer Activity, Toxicology and Histopathological Studies of the Thiolate Gold(I) Complex [Au(Spyrimidine)(PTA-CH2Ph)]Br.

A physiologically stable thiolate gold(I) derivative [Au(Spyrimidine)(PTA-CH2Ph)]Br has shown inhibition in colon cancer proliferation of Caco-2/TC7, Caco-2/PD7 and HTC-116-luc2 cell lines via apoptotic pathway and S-phase arrest in the cell cycle. Intraperitoneal injection of [Au(Spyrimidine)(PTA-CH2Ph)]Br in athymic nude mice inoculated with HTC-116-luc2 cells prolonged their survival and greatly inhibited tumour growth, near to disappearance. Low concentration of gold in urine and blood were detected in mice after 48 h of administration of 5 mg/kg body weight (bw) of the gold complex and non-organ (kidney and liver) damage has been detected after gold treatment. The results obtained suggested that the thiolate gold(I) derivative shown here could be considered as a candidate for therapeutic treatment in colon cancer.

TU-F-CAMPUS-T-03: Enhancing the Tumor Specific Radiosensitization Using Molecular Targeted Gold Nanorods

Purpose: Gold nanoparticle (GNP) mediated radiosensitization has gained significant attention in recent years. However, the widely used passive targeting strategy requires high concentration of GNPs to induce the desired therapeutic effect, thus dampening the enthusiasm for clinical translation. The purpose of this study is to utilize a molecular targeting strategy to minimize the concentration of GNPs injected while simultaneously enhancing the tumor specific radiosensitization for an improved therapeutic outcome. Methods: Cetuximab (antibody specific to the epidermal growth factor receptor that is over-expressed in tumors) conjugated gold nanorods (cGNRs) was used for the tumor targeting. The binding affinity, internalization, and in vitro radiosensitization were evaluated using dark field microscopy, transmission electron microscopy, and clonogenic cell survival assay, respectively. In vivo biodistribution in tumor (HCT116-colorectal cancer cells) bearing mice were quantified using inductively coupled plasma mass spectrometry. In vivo radiosensitization potential was tested using 250-kVp x-rays and clinically relevant 6-MV radiation beams. Results: cGNRs displayed excellent cell-surface binding and internalization (∼31,000 vs 12,000/cell) when compared to unconjugated GNRs (pGNRs). In vitro, the dose enhancement factor at 10% survival (DEF10) was estimated as 1.06 and 1.17, respectively for both 250-kVp and 6-MV beams. In vivo biodistribution analysis revealed enhanced uptake of cGNRs in tumor (1.3 µg/g of tumor tissue), which is ∼1000-fold less than the reported values using passive targeting strategy. Nonetheless, significant radiosensitization was observed in vivo with cGNRs when compared to pGNRs, when irradiated with 250-kVp (tumor volume doubling time 35 days vs 25 days; p=0.002) and 6 MV (17 days vs 13 days; p=0.0052) beams. Conclusion: The enhanced radiosensitization effect observed with very low intratumoral concentrations of gold and megavoltage x-rays using the active targeting strategy holds promise for clinical translation of this strategy from a toxicity and cost-effectiveness perspective and could evolve as a paradigm-changing approach in the field of radiation oncology.

Targeted gold nanoparticles enhance sensitization of prostate tumors to megavoltage radiation therapy in vivo

We report potent radiosensitization of prostate cancers in vitro and in vivo using goserelin-conjugated gold nanorods. Progressive receptor-mediated internalization of conjugated nanorods over time increases the radiation interaction cross-section of cells and contributes to the effects observed in vitro. The low concentrations of gold required, the long interval between injection of nanoparticles and radiation, and the use of megavoltage radiation to generate radiosensitization in vivo foretell the possibility of eventual clinical translation of this approach. From the Clinical EditorThe ability of gold nanoparticles (AuNPs) to enhance the effect of physical radiation dose on tumor cells is known. This radiosensitization effect is thought to result from an increased number of photoelectric absorption events and the increased number of electrons present in gold. The authors here sought to further increase the amount and specificity of gold accumulation in prostatic cancer cells by conjugating gold nanorods to goserelin, a synthetic luteinizing hormone releasing hormone (LHRH) analogue that would bind to the LHRH receptor overexpressed in prostate cancers. It was shown that tumour cells were more sensitive to megavoltage radiation therapy. It is hoped that there would be eventual clinical translation of this approach.

TU‐A‐9A‐05: First Experimental Demonstration of the Anisotropic Detection Principle in X‐Ray Fluorescence Computed Tomography

Purpose:To improve the sensitivity of X‐ray fluorescence computed tomography (XFCT) for in vivo molecular imaging. Is the maximum sensitivity achieved with an isotropic (4π) detector configuration? We prove that this is not necessarily true, and that a greater sensitivity is possible with anisotropic detector configuration.Methods:An XFCT imaging system was constructed consisting of 1) a collimated pencil beam x‐ray source using a fluoroscopy grade x‐ray tube; 2) a CdTe x‐ray photon counting detector to detect fluorescent x‐rays; and 3) a rotation/translation stage for tomographic imaging. We created a 6.5‐cm diameter water phantom with 2‐cm inserts of low gold concentration (0.25%–1%) to simulate tumors targeted by gold nano‐particles. The placement of x‐ray fluorescence detector were chosen to minimize scatter x‐rays. XFCT imaging was performed at three different detector positions (60°, 90°, 145°) to determine the impact of forward‐scatter, side‐scatter, and back‐scatter on imaging performance. The three data sets were also combined to estimate the imaging performance with an isotropic detector.Results:The highest imaging performance was achieved when the XF detector was in the backscatter 145° configuration. The signal‐to‐noise ratio (SNR) was 5.5 for the 0.25% gold concentration compared to SNRs of 1.4, 0, and 2.4 for 60°, 90°, and combined (60°+90°+145°) datasets. Only the 145° detector arrangement alone could detect the 0.25% concentration. The imaging dose was 14 mGy for each detector arrangement experiment.Conclusion:This study experimentally proves, for the fist time, the Anisotropic Detection Principle in XF imaging, which holds that optimized anisotropic x‐ray fluorescence detection provides greater sensitivity than isotropic detection. The optimized detection arrangement was used to improve the sensitivity of the XFCT experiment. The achieved XFCT sensitivity is the highest ever for a phantom at least this large using a benchtop x‐ray source, which is an important step toward clinical XFCT molecular imaging.This work was supported by the NCI fellowship grant R25T‐CA118681 and by the NIH (1R01‐EB016777) and NIBIB (1K99‐EB016059).

Prediction of recovery of gold thiosulfate on activated carbon using artificial neural networks

Since a high toxicity of cyanide which use as a reagent in the gold processing plant, thiosulfate has been recognized as a environmental friendly reagent for leaching of gold from ore. After gold leaching process it's important for recovery of gold from solution using adsorption or extraction methods, One of these methods is activated carbon.The loading of gold from industrial thiosulfate solution that obtained from Zarshuran gold plant-Takab-Iran, onto activated carbon have been investigated. The affecting variables of the adsorption of gold on the carbon included, temperature, concentration of gold, size of activated carbon, pH and the ratio of amount of activated carbon to the volume of solution. The results have shown that at low concentration of gold, effective loading can be achieved at pH 10.5. The size of activated carbon has a significant effect on the loading of gold. In this research the recovery of gold on activated carbon has been predicted using artificial neural network. For this purpose temperature, pH, the proportion of solution volume to weight of activated carbon, gold concentration and time of adsorption were taken as input parameters, whereas, the recovery of gold on activated carbon from thiosulfate solution was considered as an output parameter. The network with LMBP algorithm with two hidden layer were used and the topology 5-4-13-1 showed the best ability for prediction.Moreover sensitive analyze were indicated parameters pH and temperature have substantial influence on adsorption.

Growth and size distribution of Au nanoparticles in annealed Au/TiO2 thin films

Nanocomposites consisting of noble metal nanoparticles (NPs) embedded in TiO2 thin films are of great interest for applications in optoelectronics, photocatalysis and solar-cells for which the plasmonic properties of the metal NPs play a major role. This work investigates the first stages of the formation of gold NPs by thermal annealing of Au-doped TiO2 thin films grown by magnetron sputtering. A low concentration of gold in the films is considered (5at.%) in order to study the first stages of the formation of the NPs. Raman spectroscopy is used to follow the crystallization of TiO2 when increasing the annealing temperature. In addition, low-frequency Raman scattering (LFRS) is used to investigate the formation of gold NPs and to determine their size. Resonant LFRS measurements obtained by using a laser wavelength matching the surface plasmon resonance of the metallic NPs significantly enhances the Raman peak intensity enabling to focus on the first stages of the NPs formation. A double size distribution is observed at Ta=800°C calling for additional investigations by transmission electron microscopy (TEM). TEM observations reveal an inhomogeneous in-depth size distribution of gold NPs. The annealed films are structured in two sublayers with bigger NPs at the bottom and smaller NPs at the top. At Ta=800°C, a double size distribution is confirmed near the surface. A mechanism is proposed to explain the formation of the sublayers. The modification of the diffusion of gold atoms by stresses in the film near the substrate is assumed to be responsible for the observed two layers structure.

A Rapid Method for the Determination of Gold in Rocks, Ores and Other Geological Materials by F-AAS and GF-AAS After Separation and Preconcentration by DIBK Extraction for Prospecting Studies

A solvent extraction method using diisobutyle ketone (DIBK) is designed for the accurate and precise estimation of very low concentrations of gold in rocks, ores and other geological samples. 30 g sample was digested using aqua regia after roasting and gold content was extracted into DIBK phase consisting of Aliquat™ 336 and estimated by flame atomic absorption spectrometer (F-AAS). Samples having gold concentration <0.1 μg/g were estimated using graphite furnace atomic absorption spectrometer (GF-AAS). Results of DIBK extraction were compared to those obtained by other well established methods, such as classical Pb-fire assay and methyl isobutyl ketone (MIBK)-AAS methods. Comparison was also made with results obtained by the direct determination of gold by inductively coupled plasma mass spectrometry (ICP-MS) technique. The analytical results for international gold reference materials measured by the proposed method were in close agreement with those obtained by other well established methods and recommended values. Detection limits (20 ng/g by F-AAS, 0.1 ng/g by GF-AAS and 0.01 ng/g by ICP-MS) of gold (3 σ × total procedure blank) is very low and could be further improved by using high pure acids and other reagents.

Adsorption of hydrocarbons from solutions and gas phase on silica and alumina modified with silver and gold ions

The paper reports the immobilization of Ag+ cations on alumina and silica and AuCl 4 − anions on amino silica and alumina. The method of inverse gas chromatography have demonstrated that Ag(I)-silica is selective for the separation of alkanes, alkenes, alkines, and arenes. The dependence of the capacitance of Ag(I) and Au(III) composites with regard to phenylacetylene (PHA) on the nature of the carriers, surface concentration, and technique of immobilizing ion metals has been considered. The isotherms of the adsorption of PHA from solutions in octane have been measured. It has been revealed that the capacitance of composites with regard to toward PHA prepared by the immobilization of ammoniates of silver nitrate on silicon dioxide is several times higher than for composites based on alumina with the same silver concentration and composites prepared by the immobilization of silver nitrate on silicon dioxide. The capacitance of the Au(III) composite based on alumina for PHA is significantly higher than for that based on aluminum oxide. The highest capacitance for PHA (0.83 and 0.88 molecules per metal ion) is observed for Ag(I) silica and the Au(III) alumina composite. In the visible region, the diffuse reflection spectra of amino silica Au(III) composites have a significant shift of the maximum of adsorption band along with the decrease in the concentration of immobilized anions of AuCl 4 − , which evinces the formation of coordination bonds between free aminipropyl groups of the silica carrier and gold atom. The formation of these bonds prevents the adsorption of PHA on amino silica Au(III) composites with low gold concentrations.

Shear Zone-Hosted Base Metal Mineralization near Abraha Weatsebaha-Adidesta and Hawzein, Tigray Region, Northern Ethiopia

Low-grade basement rocks of Neoproterozoic age with well developed shear zones and posttectonic granitic intrusives from Hawzien area of northern Ethiopia were studied for field characteristics, mineralogy, textures, alteration assemblages and geochemistry to explore theirpotential for base metal mineralization. The basement rocks includes metavolcanic (mafic to felsic), metavolcaniclastic and metasedimentary rocks. The intrusive post-tectonic granitoids mark the end of Proterozoic. Field observation and petrographic data indicate the presence of NS, NE-SW trending shear zones; hydrothermal quartz (&plusmn;calcite) veins of different generations; malachite stains; alterations like chloritisation, kaolinization, epidotization, sericitization; and presence of base metal sulfides in association with quartz and calcite veins. Geochemistry of surface and drill core samples indicate enrichment of zinc in shear zones with low concentrations of copper, lead, gold, arsenic and silver. Zn-rich base metal mineralization with Pb-Cu-Fe (&plusmn;Ag-As-Au) is related to D2 deformation. Barite veins are although common, conspicuously occurring in E-W trending veins. Post-tectonic granitoids are facilitating the&nbsp; hydrothermal activity and the source rock compositions controlling the&nbsp; nature of the mineralization. A paragenetic scheme is suggested on the basis of texture, mineral association, alteration and deformation. Keywords: Abraha-Weatsebaha, Tigray, Ethiopia, Neoproterozoic, Shear zones, Paragenesis, Sulfide mineralization

Anti-CD30-targeted gold nanoparticles for photothermal therapy of L-428 Hodgkin&amp;#39;s cell

PurposeDue to the efficient bioconjugation and highly photothermal effect, gold nanoparticles can stain receptor-overexpressing cancer cells through specific targeting of ligands to receptors, strongly absorb specific light and efficiently convert it into heat based on the property of surface plasmon resonance, and then induce the localized protein denaturation and cell death.MethodsTwo gold nanoparticle–antibody conjugates, gold-BerH2 antibody (anti-CD30 receptor) and gold-ACT1 antibody (anti-CD25-receptor), were synthesized. Gold-BerH2 conjugates can specifically bind to the surface of L-428 Hodgkin’s cells, and gold-ACT1 conjugates were used for the control. The gold nanoparticle-induced L-428 cell-killing experiments were implemented with different experimental parameters.ResultsAt a relatively low concentration of gold and short incubation time, the influence of cytotoxicity of gold on cell viability can be overlooked. Under laser irradiation at suitable power, the high killing efficiency of gold-targeted L-428 cells was achieved, but little damage was done to nontargeted cancer cells.ConclusionGold nanoparticle-mediated photothermal therapy provides a relatively safe therapeutic technique for cancer treatment.

Comment on ‘Implications on clinical scenario of gold nanoparticle radiosensitization in regards to photon energy, nanoparticle size, concentration and location’

A recent paper by Lechtman et al (2011 Phys. Med. Biol. 56 4631–47) presented Monte Carlo modelling of gold nanoparticle dose modification. In it, they predict that the introduction of gold nanoparticles has the strongest effect with x-rays at kilovoltage energies, and that negligible increases in dose are expected at megavoltage energies. While these results are in agreement with others in the literature (including those produced by our group), the conclusion that ‘(gold nanoparticle) radiosensitization using a 6 MV photon source is not clinically feasible’ appears to conflict with recently published experimental studies which have shown radiosensitization using 6 MV x-ray sources with relatively low gold concentrations. The increasing disparity between theoretical predictions of dose enhancement and experimental results in the field of gold nanoparticle radiosensitization suggests that, while the ability of gold nanoparticles to modify dose within a tumour volume is well understood, the resulting radiosensitization is not simply correlated with this measure. This highlights the need to validate theoretical predictions of this kind against experimental measurements, to ensure that the scenarios and values being modelled are meaningful within a therapeutic context.

Synergistic enhanced photocatalytic and photothermal activity of Au@TiO2 nanopellets against human epithelial carcinoma cells

The photocatalytic and plasmonic photothermal cancer cell-killing activity of the metallic Au-capped TiO(2) (Au@TiO(2)) composite colloidal nanopellets has been investigated on HeLa cells under UV-visible (350-600 nm) light irradiation. The Au@TiO(2) composite nanopellets with the uniform Au-capped TiO(2) structure were successfully synthesized by simple reduction of HAuCl(4) on the surface of TiO(2) nanoparticles. The morphological structure and surface properties of Au@TiO(2) were characterized by using UV-visible absorption spectroscopy, TEM, SEM, XPS, EDX and XRD analyses. The formation of hydroxyl radicals (˙OH) was confirmed by photoluminescence (PL) spectra. The photocatalytic and photothermal cell-killing activity of the Au@TiO(2) nanopellets was found to vary with the molar ratio of Au to TiO(2). The direct involvement of the metal particles in mediating the electron transfer from the photoexcited TiO(2) under the band gap excitation is considered to carry out the efficient photocatalytic reaction on the cells. The plasmonic absorption spectra of Au@TiO(2) suspensions were also measured for the evaluation of photothermal cell killing. The charge separation, the interfacial charge-transfer and photothermal activity promoted the photocatalytic-photothermal cancer-cell killing more than TiO(2) alone. The cytotoxic effect of Au@TiO(2) nanopellets with low concentration of gold (TiO(2) : Au molar ratio > 1 : 1) was found to be 100%, whereas that of the commercial TiO(2) (P25) was ca. 50%. The comparative study of the cell viability using Au alone and TiO(2) alone revealed that the synergistic effect of photocatalytic hydroxyl radical formation and Au-plasmonic photothermal heat generation plays a vital role in the cancer cell killing. A plausible mechanism was also proposed for photocatalytic cancer cell killing based on the obtained results.

UNCLOAKING INVISIBLE GOLD: USE OF NANOSIMS TO EVALUATE GOLD, TRACE ELEMENTS, AND SULFUR ISOTOPES IN PYRITE FROM CARLIN-TYPE GOLD DEPOSITS

One-hundred-nm-resolution secondary ionizing mass spectrometry (nanoSIMS) was used to determine the distribution of Au, Cu, As, Sb, and S, and stable isotopes of S (34S/32S) in gold-bearing pyrite from two refractory Carlin-type gold deposits: West Banshee, northern Carlin Trend, and Turquoise Ridge, Getchell Trend, located in northern Nevada. NanoSIMS maps reveal that gold occurs in two discrete episodes in each deposit. Elevated gold concentrations correlate with elevated concentrations of As, Sb, Cu ± Te, and lower 34S/32S ratios, compared to periods when gold was not deposited. Precipitation of elevated gold and trace elements at West Banshee was followed by precipitation of pyrite with lower gold concentrations, whereas at Turquoise Ridge precipitation of trace element-rich pyrite was followed by precipitation of late ore-stage minerals. These NanoSIMS results are consistent with formation of the deposits by the episodic incursion of gold-rich fluids into hydrothermal systems otherwise dominated by gold-poor fluids. Such gold-rich fluid pulses may be related to incursions of magmatic fluid, which have been shown to have high concentrations of gold, arsenic, and copper in porphyry and high-sulfidation epithermal systems.

In situ ESR study of gold supported on NaY zeolite

AbstractElectron spin resonance (ESR) spectroscopy was used to study the anchoring of a Au complex and gold nanoparticles in NaY type zeolites. The complex of Au(II) with two nitrogen atoms of two ethylenediamine ligands [giso = 2.053, A (Au) = 16.4 G, A (N) = 15.0 G.] in the supercage of the zeolite and conduction electron spin resonance (CESR) of gold particles with 1.56‐nm diameter (g = 2.064) were observed. Their formation and stability were related with the gold concentration and the pre‐treatment conditions. The small gold particles stabilized in the supercage of zeolite were formed in the samples with low gold concentration after oxygen pre‐treatment. The confinement in the zeolite pores obviously prevents the Au(II) complex bound to two nitrogen ligands from undergoing disproportionation. Copyright © 2009 Curtin University of Technology and John Wiley &amp; Sons, Ltd.

‘Invisible gold’ in bismuth chalcogenides

Gold concentrations have been determined by LA-ICPMS in bismuth chalcogenides (tellurides and sulfosalts, minerals with modular structures; chalcogen X = Te, Se, and S) from 27 occurrences. Deposit types include epithermal, skarn, intrusion-related and orogenic gold. The samples comprised minerals of the tetradymite group, aleksite series, bismuth sulfosalts (cosalite, lillianite, hodrushite, bismuthinite, and aikinite), and accompanying altaite. Gold concentrations in phases of the tetradymite group range from <0.1 to 2527 ppm. Phases in which Bi > X tend to contain lower gold concentrations than Bi 2X 3 minerals (tellurobismuthite and tetradymite). Cosalite and lillianite contain Au concentrations ranging up to 574 and 3115 ppm, respectively. Bismuthinite derivatives have lower Au concentrations: <2 ppm in bismuthinite and up to 542 ppm in aikinite. In our samples, Au concentrations in altaite range from <0.2 to 1662 ppm. Smoother parts of the LA-ICPMS profiles suggest lattice-bound gold, whereas irregularities on the profiles are best explained by the presence of gold particles (⩽1 μm in diameter). Plotting Au vs. Ag for the entire dataset gives a wedge-shaped distribution, suggesting that Ag underpins Au uptake in both bismuth tellurides and sulfosalts. In the tellurides, correlation trends suggest statistical substitution of Ag(Au), together with Pb, into the octahedral site in the layers. In sulfosalts, Au follows coupled substitutions in which M 1+ (Ag, Cu) enters the structure. In tellurides, the presence of van der Waals gaps at chalcogen–chalcogen contacts provides for p-type semi-conductive properties critical for gold scavenging from fluids. Such weak bonds may also act as sites for nucleation of Au (nano)particles. In sulfosalts, contacts between different species that replace one another are also highly predictable to act as traps for (nano)particulate gold. Invisible gold in Bi-chalcogenides is useful to (i) identify trends of orefield zonation, (ii) discriminate between ‘melt’ and ‘fluid-driven’ scavenging, and (iii) interpret replacement and remobilisation processes. Bismuth chalcogenides have the potential to be significant Au carriers in sulfide-poor Au systems, e.g., intrusion-related gold, with impact on the overall Au budget if mean Au concentrations are high enough and the minerals are sufficiently abundant.

Synthesis, processing and forming gold structures from a 0.1 wt. % concentration solution

A very low concentration (≈0.1 wt. %) of spherical 15nm diameter gold nanoparticles were produced by the sodium citrate reduction method and later transferred to ethanol using poly vinyl pyrrolidone (PVP) as a stabilizing agent. The alcosol was then subjected to electrohydrodynamic atomisation to generate fine droplets with an average droplet diameter of < 30μm and deposited on substrates accordingly. With the assistance of various deposition methods, three different microstructures were produced. Firstly, the droplets produced by atomisation with the help of an electric field were deposited at various times on a substrate to fabricate gold films with a thickness range of ~500nm to 2000nm. Secondly, the droplets were deposited on a moving table which is computer controlled to form an array of inter-connected droplets, thus enabling us to pattern microstructures containing gold nanoparticles of different geometries (electrohydrodynamic atomisation printing). Thirdly, to reduce the track size as well as to form a dense assembly of particles in the microstructures templates were used in conjunction with electrohydrodynamic atomisation (templateassisted patterning). In order to encapsulate gold nanoparticles in a fibre a co-axial needle set-up was used with a polyethylene oxide (PEO) and polyethylene glycol (PEG) mixture as the encapsulating media. Lastly, a gold hydrosol was used to produce near-monodisperse gold microbubbles with the help of a T-junction device having an average diameter of ≈150μm. The ability to generate such a range of structures starting from a very low concentration of gold is a significant achievement.

A review of effects of silver, lead, sulfide and carbonaceous matter on gold cyanidation and mechanistic interpretation

Despite the wealth of published data on the beneficial or detrimental effects of silver, lead, sulfide, and carbonaceous matter on the rate of gold cyanidation at an anode or by dissolved oxygen, the lack of comparative studies on relative effects has hampered rationalisation of the role of these activators or passivators of gold. In the present study, the published rate data per unit surface area of gold, silver, and gold–silver alloys based on electrochemical or chemical dissolution of rotating discs or foils of constant surface area in aerated cyanide solutions at ambient temperatures are analysed on the basis of the Levich equation. The current status of the reaction mechanism is also reviewed and updated on the basis of species distribution and potential–pH diagrams, stoichiometric factors, and interim chemical species of gold(I), silver(I), and lead(II). The anodic peak potentials of reported voltammograms closely follow the potential–pH lines of Au(I)/Au(0) and Pb(II)/Pb(0) couples. Despite the formation of stable complexes between lead(II), nitrate, and hydroxide ions, the total calculated soluble lead(II) in alkaline solutions of pH range 10–11 saturated with lead hydroxide is shown to be < 0.1 g/m 3. A comparison of the reported diffusion coefficients of cyanide ions and dissolved oxygen with the values based on the Levich plots of reported rates reveals the rate-controlling stoichiometric M/CN or M/O 2 molar ratios. The difference between some of these ratios and the generally accepted ratios of M/CN = 1/2 and M/O 2 = 1/0.5 or 1/0.25 based on the formation of M(CN) 2 −, H 2O 2 or OH − in the overall cyanidation reaction is attributed to the oxidation of cyanide to cyanate and passivation due to the formation of gold hydroxides/oxides. The alloyed or dissolved silver and lead eliminate passivation due to the involvement of mixed hydroxo–cyano complexes of silver and lead ions in the surface reaction. Gold dissolution by oxygen in cyanide-rich solutions is limited by oxygen diffusion, but enhanced by the presence of a low concentration of sodium sulfide due to the involvement of hydrosulfide ion in the surface reaction. However, excess lead or sulfide retards gold cyanidation due to surface blockage by metallic lead, lead hydroxide, or due to passivation by Au 2S/S. Even low concentrations of hydrosulfide passivate gold–silver alloys due to the formation of Ag 2S. This can be eliminated by adding stoichiometric quantities of lead(II) to precipitate sulfide as PbS. Large stoichiometric ratios of O 2/M for the cyanidation of graphite coated gold appears to be a result of the enhanced oxidation of cyanide by oxygen or hydrogen peroxide, leading to a cyanide deficiency at the surface and passivation of gold by hydroxide/oxide. The presence of excess cyanide or lead(II) does not override this effect.

Contact resistance study of noble metals and alloy films using a scanning probe microscope test station

The proper selection of electrical contact materials is one of the critical steps in designing a metal contact microelectromechanical system (MEMS) switch. Ideally, the contact should have both very low contact resistance and high wear resistance. Unfortunately this combination cannot be easily achieved with the contact materials currently used in macroswitches because the available contact force in microswitches is generally insufficient (less than 1mN) to break through nonconductive surface layers. As a step in the materials selection process, three noble metals, platinum (Pt), rhodium (Rh), ruthenium (Ru), and their alloys with gold (Au) were deposited as thin films on silicon (Si) substrates. The contact resistances of these materials and their evolution with cycling were measured using a specially developed scanning probe microscope test station. These results were then compared to measurements of material hardness and resistivity. The initial contact resistances of the noble metals alloyed with Au are roughly proportional to their resistivities. Measurements of contact resistance during cycling of different metal films were made under a contact force of 200–250μN in a room air environment. It was found that the contact resistance increases with cycling for alloy films with a low concentration of gold due to the buildup of contamination on the contact. However, for alloy films with a high gold content, the contact resistance increase due to contamination is insignificant up to 108cycles. These observations suggest that Rh, Ru, and Pt and their gold alloys of low gold content are prone to contamination failure as contact materials in MEMS switches.

WE‐D‐M100J‐01: Enhancement of Cell Killing by X‐Ray Irradiation in the Presence of Gold Nanoparticles

Purpose: This investigation was initiated to determine the radiobiologic enhancement for x‐ray irradiation of cells in the presence of citrate‐stabilized gold nanoparticles. Method and materials: Citrate‐stabilized gold nanoparticles were added to a strain of lymphoma cells in suspension at a concentration of 0.017 mg of gold per ml. Cell suspensions prepared included a two sham controls, and two samples with gold nanoparticles. One sham and one gold nanoparticle based sample were irradiated with x‐ray photons from a clinical x‐ray device (120 kVp, 6.67 mm Al equivalent beam). A total dose of 0.91 Gy was delivered in two approximately equal parts (24 hour separation). The non‐irradiated cell suspensions were treated identically. Cell survival for non‐irradiated cell suspensions and irradiated cell suspensions were determined over 72 hours using methylene blue dye exclusion. Results: The ratio of live:dead cells for all cell suspensions was 7.5:1 at the start of the experiment. After 72 hours, the irradiated cells exhibited a ratio approximately 50% lower than the non‐irradiated cells. The irradiated cell suspension with gold nanoparticles showed enhanced cell killing. Conclusions: Even at the low gold concentration and low x‐ray energy, gold nanoparticles exhibit some enhancement of cell killing. Further studies are ongoing using increasing gold concentrations and varying radiation doses. It is likely that the presence of higher Z materials contributes to secondary electron dose in a way that may be described only through microdosimetry methods.Gold nanoparticle‐enhanced radiation therapy is a possible outcome of this work. Additional effort is directed toward functionalized gold nanoparticles using targeting moieties for specific cancers. This work contributes toward an understanding of the therapeutic enhancement that may be expected with specific concentrations of gold nanoparticles.Supported by: NIH R01 CA119412‐01.