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At least 19 recordsLinked to original sources
PubMed2002

In vivo liberation of gold ions from gold implants. Autometallographic tracing of gold in cells adjacent to metallic gold.

For some years, the implantation of small pieces of gold has been used as an unauthorised remedy for osteoarthritis and pain. The aim of the present study was to evaluate whether gold ions are released from gold implants. Pieces of pure gold were placed in the connective tissue of skin, bone and brains of anaesthetised animals. Ten days to several months later the animals were anaesthetised and killed by transcardial perfusion. Tissue blocks containing the gold pieces were cut, and the sections were silver-enhanced by autometallography. It was found that gold ions are released from the implanted gold and diffuse out into the surrounding tissue. The gold-containing cells in connective tissues were macrophages, mast cells and fibroblasts. In the brain, gold accumulated in astrocytes and neurons. Proton-induced X-ray emission spectroscopy analysis of the tissue surrounding gold implants confirmed that gold ions are liberated. The findings suggest that the gold implant technique, on a local scale, mimics systemic treatment with a gold-containing drug.

Animals↗
PubMed2002

Gold concentration in blood in relation to the number of gold restorations and contact allergy to gold.

Previous studies have demonstrated an association between gold allergy and the presence of dental gold restorations. The aim of the present study was to investigate the relationship between the concentration of gold in blood (B-Au) and the number of tooth surfaces with gold alloys in subjects with and without contact allergy to gold. In 80 patients referred for patch testing because of eczematous disease, blood samples were taken and analyzed for B-Au using inductively coupled plasma mass spectrometry. The detection limit for the Au determination was 0.04 microg/L. In addition, a dentist made a clinical and radiological examination of the patients and registered the number of dental gold surfaces. Patients with dental gold restorations had a statistically significantly higher B-Au in Mann-Whitney U test (P = 0.025), (range < 0.04-1.07 microg/L) than patients without (range < 0.04-0.15 microg/L). Furthermore, a positive correlation was found between B-Au and the number of dental gold surfaces (P < 0.01). There was no statistically significant difference in B-Au between persons with and without contact allergy to gold. The study thus indicates that gold is released from dental restorations and taken tip into the circulation.

Acrylic Resins↗
PubMed1998

Action of gold chloride ("gold toning") on silver-enhanced 1 nm gold markers.

In conventional immunoelectron microscopy (IEM), very small colloidal gold particles (0.8-3 nm), or the gold compound Nanogold (1.4 nm) are silver-enhanced for easy detection. However, silver enhancement has drawbacks. First, the silver layer is dissolved during fixation with osmium tetroxide, even if the concentration and incubation time are strongly reduced during pre-embedding labeling experiments in transmission electron microscopic (TEM) and scanning electron microscopic (SEM) studies. Second, after exposure to the electron beam the silver layer may migrate on the section or the whole particles may disappear. Sometimes silver migration can be observed even without irradiation. This effect strongly hampers reinvestigation of previously inspected areas, after some time of storage. In both cases, gold chloride treatment after silver enhancement is sufficient to completely protect the silver-enhanced 1 nm gold markers. Gold chloride treatment is part of the so-called "gold toning" procedure, which is a method used to substitute and/or cover the silver by a layer of gold. It can be applied in TEM and SEM experiments. As a serious drawback, gold chloride treatment slightly reduces the size of both unenhanced and silver-enhanced gold particles and can lead to disintegrated silver/gold particles. Therefore, this technique is useful for pre-embedding IEM, on-(resin)section, and ultrathin cryosection labeling experiments. However, it appears to be unsuitable for double-labeling studies using different gold sizes, for quantitation experiments, and in SEM.

Cryoultramicrotomy↗
PubMed2005

Gold trichloride and gold sodium thiosulfate as markers of contact allergy to gold.

The usefulness of a trivalent gold salt, gold trichloride (GTC), was evaluated as a marker of contact allergy to gold. Patients patch test-positive or patch test-negative to gold sodium thiosulfate (GSTS), 13 subjects of each, were patch tested with dilution series of GTC and equimolar concentrations of GSTS. In order to avoid false-positive and false-negative test reactions, the salts were buffered and placed on polypropene chambers. Allergic reactions were registered in 9/13 gold-allergic patients with GSTS and in 2/13 with GTC. The sum of positive reactions was 18 with GSTS and 5 with GTC. Irritant reactions were none with GSTS and 2 with GTC in the gold-allergic patients. It is concluded that GTC can elicit positive patch test reactions in patients with gold allergy but to a lesser degree when compared with GSTS. Thus, GTC cannot be recommended in patch testing, and GSTS is still the test agent of choice.

Aged↗
PubMed1991

Gold enhancement of gold-labeled probes: gold-intensified staining technique (GIST).

In this report we present a staining method in which gold chloride is used to enhance the size of gold colloids. We show the utility of this technique when used in conjunction with small gold colloids, i.e., 5 nm, 4 nm, and 2.6 nm. Post-embedding staining of epoxy-embedded, gold-labeled mouse LM fibroblasts showed that staining with 0.1% gold chloride facilitated the visualization of the smallest gold colloids.

Animals↗
PubMed2001

Structural variations and bonding in gold halides: a quantum chemical study of monomeric and dimeric gold monohalide and gold trihalide molecules, AuX, Au2X2, AuX3, and Au2X6 (X = F, Cl, Br, I).

The molecular structures of all gold mono- and trihalides and of their dimers have been calculated at the B3LYP, MP2, and CCSD(T) levels of theory by using relativistic pseudopotentials for all atoms except fluorine. Our computations support the experimental observation that the relative stability of the monohalides increases from the fluoride toward the iodide, while the stability trend of the trihalides is the opposite. The potential energy surface (PES) of all gold trihalides has been investigated. These molecules are typical Jahn-Teller systems; the trigonal planar D3h-symmetry geometry does not correspond to the minimum energy structure for any of them. At the same time, the amount and character of their Jahn-Teller distortion changes gradually from AuF3 to AuI3. The minimum energy geometry is a T-shaped structure for AuF3 and AuCl3, with a Y-shaped transition-state structure. For AuI3, the Y-shaped structure lies lower than the T-shaped structure on the PES. For AuBr3 and AuI3, neither of them is the global minimum but instead an L-shaped structure, which lies outside the Jahn-Teller PES. This structure can be considered to be a donor-acceptor system, or a closed-shell interaction, with I2 acting as donor and AuI as acceptor. The dimers of gold monohalides have very short gold-gold distances and demonstrate the aurophilic interaction. The dimers of the trihalides are planar molecules with two bridging halogen atoms.

Journal Article↗
PubMed2004

Molecular design of luminescence ion probes for various cations based on weak gold(I)...gold(I) interactions in dinuclear gold(I) complexes.

A series of luminescent dinuclear gold(I) complexes with different crown ether pendants, [Au(2)(PwedgeP)(S-B15C5)(2)] [S-B15C5 = 4'-mercaptobenzo-15-crown-5, P(wedge)P = bis(dicyclohexylphosphino)methane (dcpm) (1), bis(diphenylphosphino)methane (dppm) (2)] and [Au(2)(P(wedge)P)(S-B18C6)(2)] [S-B18C6 = 4'-mercaptobenzo-18-crown-6, P(wedge)P = dcpm (3), dppm (4)], and their related crown-free complexes, [Au(2)(P(wedge)P)(SC(6)H(3)(OMe)(2)-3,4)(2)] [P(wedge)P = dcpm (5), dppm (6)], were synthesized. The low-energy emission of the mercaptocrown ether-containing gold(I) complexes are tentatively assigned as originated from states derived from a S --> Au ligand-to-metal charge transfer (LMCT) transition. The crown ether-containing gold(I) complexes showed specific binding abilities toward various metal cations according to the ring size of the crown pendants. Spectroscopic evidence was provided for the metal-ion-induced switching on of the gold...gold interactions upon the binding of particular metal ions in a sandwich binding mode.

Journal Article↗
PubMed2002

Advanced mercury removal from gold leachate solutions prior to gold and silver extraction: a field study from an active gold mine in Peru.

Mercury contamination in the Gold-Cyanide Process (GCP) is a serious health and environmental problem. Following the heap leaching of gold and silver ores with NaCN solutions, portions of the mercury-cyano complexes often adhere to the activated carbon (AC) used to extract the gold. During the electrowinning and retorting steps, mercury can be (and often is) emitted to the air as a vapor. This poses a severe health hazard to plant workers and the local environment. Additional concerns relate to the safety of workers when handling the mercury-laden AC. Currently, mercury treatment from the heap leach solution is nonexistent. This is due to the fact that chelating ligands which can effectively work under the adverse pH conditions (as present in the heap leachate solutions) do not exist. In an effort to economically and effectively treat the leachate solution prior to passing over the AC, a dipotassium salt of 1,3-benzenediamidoethanethiol (BDET2-) has been developed to irreversibly bind and precipitate the mercury. The ligand has proven to be highly effective by selectively reducing mercury levels from average initial concentrations of 34.5 ppm (parts per million) to 0.014 ppm within 10 min and to 0.008 ppm within 15 min. X-ray powder diffraction (XRD), proton nuclear magnetic resonance (1H NMR), Raman, and infrared (IR) spectroscopy demonstrate the formation of a mercury-ligand compound, which remains insoluble over pH ranges of 0.0-14.0. Leachate samples from an active gold mine in Peru have been analyzed using cold vapor atomic fluorescence (CVAF) and inductively coupled plasma optical emission spectroscopy (ICP-OES) for metal concentrations before and after treatment with the BDET2- ligand.

Carbon↗
PubMed2005

Glutathione-protected gold clusters revisited: bridging the gap between gold(I)-thiolate complexes and thiolate-protected gold nanocrystals.

Small gold clusters (approximately 1 nm) protected by molecules of a tripeptide, glutathione (GSH), were prepared by reductive decomposition of Au(I)-SG polymers at a low temperature and separated into a number of fractions by polyacrylamide gel electrophoresis (PAGE). Chemical compositions of the fractionated clusters determined previously by electrospray ionization (ESI) mass spectrometry (Negishi, Y. et al. J.Am. Chem. Soc. 2004, 126, 6518) were reassessed by taking advantage of freshly prepared samples, higher mass resolution, and more accurate mass calibration; the nine smallest components are reassigned to Au10(SG)10, Au15(SG)13, Au18(SG)14, Au22(SG)16, Au22(SG)17, Au25(SG)18, Au29(SG)20, Au33(SG)22, and Au39(SG)24. These assignments were further confirmed by measuring the mass spectra of the isolated Au:S(h-G) clusters, where h-GSH is a homoglutathione. It is proposed that a series of the isolated Au:SG clusters corresponds to kinetically trapped intermediates of the growing Au cores. The relative abundance of the isolated clusters was correlated well with the thermodynamic stabilities against unimolecular decomposition. The electronic structures of the isolated Au:SG clusters were probed by X-ray photoelectron spectroscopy (XPS) and optical spectroscopy. The Au(4f) XPS spectra illustrate substantial electron donation from the gold cores to the GS ligands in the Au:SG clusters. The optical absorption and photoluminescence spectra indicate that the electronic structures of the Au:SG clusters are well quantized; embryos of the sp band of the bulk gold evolve remarkably depending on the number of the gold atoms and GS ligands. The comparison of these spectral data with those of sodium Au(I) thiomalate and 1.8 nm Au:SG nanocrystals (NCs) reveals that the subnanometer-sized Au clusters thiolated constitute a distinct class of binary system which lies between the Au(I)-thiolate complexes and thiolate-protected Au NCs.

Electrophoresis, Polyacrylamide Gel↗
PubMed1999

Prevalence of gold sensitivity in asymptomatic individuals with gold dental restorations.

BACKGROUND: The clinical relevance of positive patch test reactions to gold sodium thiosulfate in asymptomatic individuals with gold dental restorations is often unclear. Knowledge of the prevalence of gold sensitivity in individuals with and without gold dental restorations is required to better understand the relevance of these reactions. OBJECTIVE: To determine the prevalence of positive patch test reactions to gold in asymptomatic individuals with gold dental restorations (gold patients) compared with similar individuals without gold dental appliances (nongold patients). METHODS: One hundred thirty-six healthy, asymptomatic patients were patch tested to gold sodium thiosulfate, nickel sulfate and palladium chloride. Readings occurred after 2 days and 7 days. RESULTS: Of the patients tested, 24 of 71 (33.8%) gold patients had a positive reaction to gold versus 7 of 65 (10.8%) of the nongold patients, P <.001. Of those with a positive gold reaction, 12 of 31 (38.7%) also had a positive nickel reaction. Nickel alone was positive in 18 of 71 (25. 4%) of gold patients versus 11 of 65 (16.9%) of nongold patients. 19 of 29 (65.5%) of those with a positive nickel reaction also reacted to palladium and 19 of 22 (86.4%) of those with a palladium reaction also reacted to nickel. The rate of allergy to gold computed over a 3-year period for patients patch tested in the Oregon Health Sciences University (OHSU) Contact Dermatitis Clinic was 13.5% (46/342). CONCLUSIONS: The prevalence of gold sensitivity in individuals with gold dental restorations is approximately 33.8%. This is significantly greater than the 10.8% prevalence seen in individuals without gold dental appliances, as well as greater than the 3-year rate from the OHSU Contact Dermatitis Clinic. This data should help shed light on issues of clinical relevance.

Adult↗
PubMed1992

Characterization of gold in urine and bile following administration of gold sodium thiomalate with chelating agents to rats.

Gold was characterized in the urine and bile of rats treated with D-penicillamine (D-PEN), 2,3-dimercaptosuccinic acid (DMSA), 2,3-dimercaptopropane sulphonate (DMPS), or N-(2-mercapto-2-methylpropanoyl)-L-cysteine (bucillamine) immediately after gold sodium thiomalate (AuTM) injection by both gel chromatographic and electrophoretic methods. It is suggested that the gold in the urine and bile after AuTM administration was predominantly bound to high molecular weight compounds. The characterization of gold in the urine after administration of AuTM with D-PEN, DMSA, or DMPS showed that most of the gold was bound to the chelating agents. In the treatment with the chelating agents such as D-PEN and DMPS, the gold was mainly excreted as a gold-chelating agent compound in the bile and a minor portion of the gold was present in the form of a gold-L-cysteine compound and high molecular weight compounds. DMSA treatment showed that a major portion of the gold was bound to high molecular weight compounds in the bile and a minor portion of the gold was present in the forms of gold-DMSA and gold-L-cysteine compounds. The administration of AuTM and bucillamine indicated that the gold was mainly present as a gold-Me-bucillamine compound in the urine and a gold-bucillamine compound in the bile.

Animals↗
PubMed2000

Evidence of gold-gold intra- and intermolecular interactions gained by laser desorption/ionisation and fast atom bombardment mass spectrometry in the study of some gold(I) coordination compounds

The mass spectrometric behaviour of some two-coordinated linear gold(I) complexes has been studied by fast atom bombardment (FAB) and laser desorption/ionisation (LDI) methods. The results obtained demonstrate some interesting aspects of Au-Au interactions. The detection under FAB conditions of Au(n)(+) clusters, in particular of Au(3)(+) species, can be rationalised by the presence of significant intramolecular Au-Au interactions, while the formation under LDI conditions of Au(n)(+) clusters can be considered indicative of Au(ellipsis)Au intermolecular interactions present in the solid state. Copyright 2000 John Wiley & Sons, Ltd.

Journal Article↗
PubMed1996

Solid State Structures and Gold-Gold Bonding in Luminescent Halo(dimethylphenylphosphine)gold(I) Complexes.

The structures of the series of two-coordinate gold(I) complexes {(Me(2)PhP)AuX}(n) where X is Cl, Br, or I have been examined by X-ray diffraction. The chloro complex crystallized in two separate polymorphic forms. Colorless hexagonal blocks of {(Me(2)PhP)AuCl}(3) crystallized in the monoclinic space group P2(1)/m with a = 12.141(4) Å, b = 8.433(2) Å, c = 14.834(3) Å, and beta = 94.15(2) degrees at 130 K with Z = 2. Refinement of 2837 reflections and 177 parameters yielded R = 0.066 and R(w) = 0.069. The complex consists of three nearly linear P-Au-Cl units that are connected by Au-Au contacts at 3.091(2) and 3.120(2) Å. Colorless prisms of {(Me(2)PhP)AuCl}(2) form in the orthorhombic space group P2(1)2(1)2(1) as described earlier (Cookson, P. D.; Tiekink, E. R. T. Acta Crystallogr. 1993, C49, 1602). The two nearly linear P-Au-Cl units are staggered and connected through a Au-Au bond (3.230(2) Å). Colorless rectangular prisms of {(Me(2)PhP)AuBr}(2) form in the monoclinic space group P2(1) with a = 9.572(5) Å, b = 8.757(3), and c = 12.915(7) at 130 K with Z = 2. Refinement of 2469 reflections with 118 parameters yielded R = 0.080 and R(w) = 0.084. {(Me(2)PhP)AuI}(2) is isomorphous with the bromo complex with a = 9.736(2) Å, b = 8.890(2) Å, and c = 13.160(5) Å at 130 K with Z = 2. Refinement of 2796 reflections with 119 parameters yielded R = 0.052 and R(w) = 0.058. These complexes are similar to the chloro dimer but with altered orientations of the phenyl substituent. The predicted order of ligand effects (Cl > Br > I) on Au-Au distances from quasi-relativistic calculations is borne out in the experimental values: 3.230 Å (Cl); 3.119 Å (Br); 3.104 Å (I). In dichloromethane, these complexes dissociate into monomeric units but there is some evidence for the presence of dimers in concentrated solutions of the iodide compound.

Journal Article↗
PubMed2002

Catalytic role of gold in gold-based catalysts: a density functional theory study on the CO oxidation on gold.

Gold-based catalysts have been of intense interests in recent years, being regarded as a new generation of catalysts due to their unusually high catalytic performance. For example, CO oxidation on Au/TiO(2) has been found to occur at a temperature as low as 200 K. Despite extensive studies in the field, the microscopic mechanism of CO oxidation on Au-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Au, we have performed extensive density functional theory calculations for the elementary steps in CO oxidation on Au surfaces. O atom adsorption, CO adsorption, O(2) dissociation, and CO oxidation on a series of Au surfaces, including flat surfaces, defects and small clusters, have been investigated in detail. Many transition states involved are located, and the lowest energy pathways are determined. We find the following: (i) the most stable site for O atom on Au is the bridge site of step edge, not a kink site; (ii) O(2) dissociation on Au (O(2)-->2O(ad)) is hindered by high barriers with the lowest barrier being 0.93 eV on a step edge; (iii) CO can react with atomic O with a substantially lower barrier, 0.25 eV, on Au steps where CO can adsorb; (iv) CO can react with molecular O(2) on Au steps with a low barrier of 0.46 eV, which features an unsymmetrical four-center intermediate state (O-O-CO); and (v) O(2) can adsorb on the interface of Au/TiO(2) with a reasonable chemisorption energy. On the basis of our calculations, we suggest that (i) O(2) dissociation on Au surfaces including particles cannot occur at low temperatures; (ii) CO oxidation on Au/inactive-materials occurs on Au steps via a two-step mechanism: CO+O(2)-->CO(2)+O, and CO+O-->CO(2); and (iii) CO oxidation on Au/active-materials also follows the two-step mechanism with reactions occurring at the interface.

Journal Article↗
PubMed1992

Activation of gold-reactive T lymphocytes in rheumatoid arthritis patients treated with gold.

OBJECTIVE: To assess the role of T lymphocyte sensitization in the etiology of side effects of gold therapy in patients with rheumatoid arthritis (RA). METHODS: Lymphocyte proliferation induced by gold(III) and gold(I) salts was measured in 53 subjects: 30 RA patients with gold-induced side effects (17 with dermatitis, 9 with proteinuria, 3 with hematologic complications, and 1 with colitis), 9 RA patients without side effects despite prolonged chrysotherapy, 4 RA patients who had never received gold, and 10 healthy controls. Peripheral blood lymphocytes were cultured with the different gold salts and proliferation was measured by 3H-thymidine incorporation. RESULTS: Thirteen of the 17 RA patients who developed gold-induced dermatitis showed significant T lymphocyte proliferation in response to gold(III) salts, and this proliferation could be completely blocked by monoclonal antibodies directed at the HLA-DR molecule. Such proliferative responses were not seen in patients with other gold-induced side effects, in patients who had never received gold, or in healthy controls. Only 1 of 9 patients who had not developed side effects despite long-term maintenance chrysotherapy showed significant lymphocyte activation with gold(III) salts. Lymphocyte proliferation could not be induced with gold(I) salts or with other metal salts. CONCLUSION: Patients with RA who develop dermatitis following treatment with sodium aurothiomalate [gold(I)] have T cells which proliferate in an HLA-DR-restricted manner in response to HAuCl4 [gold(III)]. We believe this observation can lead to more accurate diagnosis and treatment of side effects, which currently limit the use of one of the most effective antirheumatic drugs.

Adult↗
PubMed1986

Inter-strand cross-links and single-strand breaks produced by gold(I) and gold(III) coordination complexes.

The ability of gold coordination complexes to bind to DNA and produce inter-strand cross-links in DNA was assessed in an assay system based on the fluorescence properties of the DNA intercalative dye, ethidium bromide. Results from these studies using a variety of gold(I) and gold(III) complexes suggest that the ability of gold complexes to bind to and produce inter-strand cross-links in DNA is not dependent on the oxidation state of gold in the complex but is influenced by the nature of the coordinating ligands. Those complexes in which the gold was ligated through one or more weakly coordinating ligands showed evidence for DNA binding. However, only those complexes with two or more of these relatively weak coordinating ligands produced inter-strand cross-links. Both the amount of binding to and cross-linking of DNA by these compounds were decreased by treatment of the gold-DNA complex with 2-mercaptoethanol and other thiol containing agents. As shown by agarose gel electrophoresis, 2-mercaptoethanol caused a dissociation of the gold-DNA complexes and a regeneration of closed circular superhelical pBR322 DNA. DNA strand breakage also resulted from treatment of a number of gold-DNA complexes with 2-mercaptoethanol; this was observed with the gold compounds which were shown to produce inter-strand cross-links in DNA. The amount of DNA strand breakage produced by treatment of gold-DNA complexes with 2-mercaptoethanol was influenced by the initial conformation of the DNA; gold-DNA complexes which resulted from the binding of gold compounds to covalently closed superhelical DNA were more sensitive to the breakage induced by 2-mercaptoethanol treatment than those complexes in which closed circular, relaxed DNA was used as substrate. The DNA breakage was not reduced in partially anaerobic conditions or by free-radical scavengers, suggesting that it is not mediated by oxygen. The results are discussed with respect to the potential for the interaction of gold complexes with intracellular DNA and chromatin and their biological implications.

Anaerobiosis↗
PubMed1992

Effective diameters of protein A-gold and goat anti-rabbit-gold conjugates visualized by field emission scanning electron microscopy.

High-voltage (15-30 kV) field emission scanning electron microscopy (FESEM) was used to evaluate the effects of gold particle size and protein concentration on the formation of protein-gold complexes. Six colloidal gold sols were prepared, ranging in diameter from 7.6 to 39.8 nm. The minimal protecting amounts (m.p.a.) of protein A and goat anti-rabbit antibody (GAR) were experimentally determined. Gold particles were conjugated at the m.p.a., one half the m.p.a., and ten times the m.p.a. for both proteins, and protein-gold complexes prepared for FESEM. The smallest colloidal gold particles required the most protein per milliliter of gold suspension for stabilization. Transmission electron microscopy was found to be the preferred method for accurate sizing of gold particles, whereas FESEM of protein-gold complexes permitted visualization of a protein halo around a spherical gold core. Protein halo width varied significantly with changes in gold particle size. Measurements of protein halos indicated that conjugation with the m.p.a. of protein A resulted in the thickest protein layers for all gold sizes. GAR conjugation with the m.p.a. again produced the thickest protein layers. However, GAR halos were significantly smaller than those obtained with protein A conjugation. The proteins used showed similar adsorption patterns for the larger gold particles. For smaller gold particles, proteins may act differently, and these complexes should be further characterized by low-voltage FESEM.

Animals↗