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[Pneumonitis caused by gold salts in psoriatic arthritis: report of 2 cases].

The gold-salts compounds have been used for the treatment of rheumatoid arthritis and of psoriatic arthritis, they are generally tolerates and when have adverse effects they are minor. The gold-induced lung toxicity is a infrequent adverse effect of patients with rheumatoid arthritis characterized by three types: interstitial penumonitis, bronchiolitis obliterans with organizing pneumonia and bronchiolitis obliterans, usually the first is the more frequent. The diagnostic is supported by the clinical manifestations, chest roentgenogram, bronchoalveolar lavage fluid and chest computed tomography scan. Biopsy study of the lung, is only needed for exclusion of other pulmonary disease. The gold-induced lung toxicity in the psoriatic arthritis is rarelly described, we report two cases with gold-induced pneumonitis with benign clinical course after cessation of therapy and treatment with corticosteroids.

Antirheumatic Agents↗

Gold dermatitis due to ear piercing: correlations between gold and mercury hypersensitivities.

A case of allergic contact dermatitis due to gold pierced earrings is reported. The patient developed recurring redness and swelling on her earlobes a month after the wearing of pierced-type gold earrings, which was followed by the appearance of reddish nodules around the puncture marks. Patch tests revealed positive reactions to 0.1% mercuric chloride, 1% gold sodium thiomalate and 0.2% chloroauric acid. We also demonstrated that guinea pigs contact-sensitized with a mercuric compound developed positive patch test reactions to both mercuric and gold compounds. These results suggest that there may be correlations between gold and mercury hypersensitivities.

Adult↗

Pentahapto-bonded gold heteroborane clusters [3-(R3P)-closo-2,1-AuTeB10H10]- and [3-(R3P)-closo-3,1,2-AuAs2B9H9]-.

Gold acetylide compounds [(R3P)AuC[triple bond]CC(Me)(OH)Et], where R = Ph 1 or cyclohexyl (Cy) 2, were synthesised and 2 was characterised using X-ray diffraction techniques. The solid-state structure of 2 contained a two-coordinate gold atom and a linear P-Au-C[triple bond]C-C bonding sequence. The reactions between 1 or 2 and [NR4][nido-7,8-As2B9H10] or [NR4][nido-7-TeB10H10] in ethanol-acetone solvent afforded the twelve-vertex cluster species [NMe4][3-(R3P)-closo-3,1,2-AuAs2B9H9], where R = Ph 5 or Cy 6, or [NEt4][3-(R3P)-closo-2,1-AuTeB10H10], where R = Ph 7 or Cy 8, in moderate or low yields (ca. 35% for , and and ca. 20% for ). Compounds and were characterised with X-ray crystallographic techniques. Although there was crystallographic disorder in the {As2B3} and {TeB4} rings to which the gold atoms were attached, the structures of 5 and 7 strongly suggested that the gold atoms were pentahapto bonded to all the atoms in the {As2B3} or {TeB4} rings giving formally closo cluster geometries with closo cluster electron counts. The solution-phase NMR properties of 5, 6 and 7 were consistent with closo descriptions.

Journal Article↗

Reductive precipitation of gold by dissimilatory Fe(III)-reducing bacteria and archaea.

Studies with a diversity of hyperthermophilic and mesophilic dissimilatory Fe(III)-reducing Bacteria and Archaea demonstrated that some of these organisms are capable of precipitating gold by reducing Au(III) to Au(0) with hydrogen as the electron donor. These studies suggest that models for the formation of gold deposits in both hydrothermal and cooler environments should consider the possibility that dissimilatory metal-reducing microorganisms can reductively precipitate gold from solution.

Archaea↗

Who invented 'Avicenna's gilded pills'?

This article questions the belief expressed in various histories of pharmacy that the tenth-century Arab physician Avicenna introduced the tradition of coating pills with gold and silver. Although an examination of his Canon documents Avicenna's interest in the medicinal application of gold and silver, no mention is made of coating pills. Nor do other Islamic physicians seem to have been familiar with this practice, any more than such medieval European authors as Arnaldus of Villanova, Raymund Lull or Johannes de Rupescissa. The same is true of medicinal compendia representative of later periods, such as the Ortus sanitatis, Valerius Cordus' Dispensatorium or the Secrets of Alessio Piemontese. The earliest known mention of coating pills with precious metals occurs in a non-medical book, The Golden Fleece (London, 1626), and the earliest mention in the professional literature seems to appear only in the second half of the seventeenth century. The practice of coating pills with gold and silver was to be practiced in Europe into the first half of the twentieth century.

Drug Compounding↗

Synthesis and redox behavior of biferrocenyl-functionalized ruthenium(II) terpyridine gold clusters.

Spectroscopic and electrochemical characterizations of ferrocene- and biferrocene-functionalized terpyridine octanethiolate monolayer-protected clusters were investigated and reported. The electrochemical measurements of Ru2+ coordinated with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine complexes were dominated by the Ru2+/Ru3+ redox couple (E(1/2) at approximately 1.3 V), Fe(2+)/Fe(3+) redox couples (E(1/2) from approximately 0.6 to approximately 0.9 V), and terpy/terpy-/terpy2- redox couples (E(1/)(2) at ca. -1.2 and ca. -1.4 V). The substantial appreciable variations detected in the Ru2+/Ru3+ and Fe2+/Fe3+ oxidation potentials indicate that there is an interaction between the Ru2+ and Fe2+ metal centers. The coordination of the Ru2+ metal center with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine leads to an intense 1[(d(pi)Fe)6] --> 1[d(pi)Fe)5(pi*terpyRu)1] transition in the visible region. The 1[(d(pi)Fe)6] -->1[d(pi)Fe)5(pi*terpyRu)1] transition observed at approximately 510 nm revealed that there was a qualitative electronic coupling between metal centers. The coordination of the Ru2+ transition metal center lowers the energy of the pi*terpy orbitals, causing this transition.

Electrochemistry↗

Spectrophotometric studies of the interaction of noble metals with quercetin and quercetin-5'-sulfonic acid.

Results of some studies on the interaction of noble metals with quercetin (Q) and quercetin-5'-sulfonic acid (QSA), the compounds of flavonoid group, are presented. The reactions of chloride complexes of the metals: RuOHCl5(2-), PdCl4(2-), OsCl6(2-), PtCl6(2-) and AuCl4- with both reagents were examined. The redox reactions of ruthenium and gold with Q and QSA have been identified. The reaction of the metals with both reagents results in the formation of the oxidized form of Q that exhibits maximum absorbance at 291 nm. Ruthenium and gold react with the examined reagents under similar conditions: 0.04 M HCl and 1 x 10(-4) M Q (or QSA). The CH3OH + H2O (1:1) (Q) and pure aqueous (QSA) media can be used. The reaction of gold with Q is slow at room temperature. It can be accelerated by heating the solution being examined. The reaction proceeds significantly faster when the water-soluble sulfonic derivative of quercetin, quercetin-5'-sulfonic acid, is used as a reagent. The new species formed can make the basis of spectrophotometric methods for the determination of ruthenium and gold. The molar absorptivities at 291 nm are equal to 5.0 x 10(3) and 2.2 x 10(4) L mol(-1) cm(-1) for Ru and Au, respectively, independently of the reagent used. Some methods for the determination of the content of gold (0.04%) in a cosmetic cream were developed.

Cosmetics↗

Do gold drugs inhibit interleukin-1? Evidence from an in vitro lymphocyte activating factor assay.

The ability of some antiarthritic gold (I) compounds to inhibit the in vitro lympho-proliferative activity of human interleukin-1 (IL-1) in the lymphocyte activating factor (LAF) assay was investigated. Marked inhibition was seen at concentrations of auranofin (AF) and gold sodium thiomalate (GSTM) that correspond to gold levels found in the serum of patients receiving these drugs. This inhibition was not due to direct inactivation of the IL-1 molecule. Omitting 2-mercaptoethanol from the LAF assay potentiated the effect of GSTM. The antiproliferative effect of AF occurs almost immediately and probably reflects its direct cytotoxicity to stimulated lymphocytes.

Animals↗

Gold(III) dithiocarbamate derivatives for the treatment of cancer: solution chemistry, DNA binding, and hemolytic properties.

Gold(III) compounds are emerging as a new class of metal complexes with outstanding cytotoxic properties and are presently being evaluated as potential antitumor agents. We report here on the solution and electrochemical properties, and the biological behavior of some gold(III) dithiocarbamate derivatives which have been recently proved to be one to 4 orders of magnitude more cytotoxic in vitro than the reference drug (cisplatin) and to be able to overcome to a large extent both intrinsic and acquired resistance to cisplatin itself. Their solution properties have been monitored in order to study their stability under physiological conditions; remarkably, they have shown to undergo complete hydrolysis within 1 h, the metal center remaining in the +3 oxidation state. Their DNA binding properties and ability in hemolyzing red blood cells have been also evaluated. These gold(III) complexes show high reactivity toward some biologically important isolated macromolecules, resulting in a dramatic inhibition of both DNA and RNA synthesis and inducing DNA lesions with a faster kinetics than cisplatin. Nevertheless, they also induce a strong and fast hemolytic effect (compared to cisplatin), suggesting that intracellular DNA might not represent their primary or exclusive biological target.

Animals↗

Kinetics of reduction of nitrobenzene and carbon tetrachloride at an iron-oxide coated gold electrode.

The rates of reduction of carbon tetrachloride (CT) and nitrobenzene (NB) by iron-oxide coated gold electrodes were studied to gain insight into the processes that control reduction of groundwater contaminants by zerovalent metal permeable reactive barriers. Fe(III)-oxide films were deposited on gold electrodes with a small fraction of the Fe(III) electrochemically reduced to Fe(II) to investigate the role of Fe(II) in the reduction of the CT and NB. Mass transport to the surface of the oxide film was controlled through use of a well-defined flow-through system similar to a wall-jet electrode. The factors affecting the overall reduction rate were investigated by varying the Fe(II) content in the iron-oxide, controlling mass transport of the electroactive species to the oxide surface, and varying the thickness of the oxide film. The rates of reduction of CT and NB were found to be independent of Fe(II) content in the iron-oxide and were only slightly dependent on the rate of transport to the surface of the oxide under a few sets of reaction conditions. Conversely, the rates of reduction were greatly dependent on the thickness of the oxide film, with the reduction rate decreasing as the oxide thickness increased. Evidence suggests that the location of the reduction reaction for CT and NB is at the gold surface and supports a barrier model for the system studied, in which the oxide film physically impedes direct contact of the electroactive species and the gold electrode, increases the diffusion path length, and creates adsorption sites.

Adsorption↗

Study of peptide dendrimers having a ferrocene core supported on mercaptoundecanoic acid.

Hydrogen-bonding interactions between the carboxylic acid groups of mercaptoundecanoic acid (MUA) coated gold substrates and the ester surface of peptide dendrimers allows the formation of glutamic acid dendrimers films. Dendrimer films were prepared for generations 1-6 (G1-G6) and analyzed by spectroscopic and electrochemical techniques. Electrochemical studies using cyclic voltammetry and differential pulse voltammetry show that all films except those of G6 were electrochemically active. Lack of activity of G6 films is rationalized by the total encapsulation of the ferrocene redox probe by the dendritic sheath and lack of ion pairing, which prevents its oxidation.

Dendrimers↗

Gram-scale synthesis of soluble, near-monodisperse gold nanorods and other anisotropic nanoparticles.

An aqueous surfactant-based colloidal chemical method is reported for the synthesis of anisotropic noble-metal nanoparticles on the milligram to multigram scale. Fine control of the nucleation-growth kinetics and rodlike micelle-induced breaking of symmetry at the early stage of particle growth are responsible for high-quality anisotropic nanoparticles. Near-monodisperse gold and silver nanorods, spheroids, nanowires, platelets, or cubes of 4-50 nm dimension and controllable aspect ratio can be prepared. The method may also be extended to semiconductor systems.

Anisotropy↗

Gold and gold-iron oxide magnetic glyconanoparticles: synthesis, characterization and magnetic properties.

The preparation, characterization and the magnetic properties of gold and gold-iron oxide glyconanoparticles (GNPs) are described. Glyconanoparticles were prepared in a single step procedure in the presence of aqueous solution of thiol functionalized neoglycoconjugates and either gold salts or both gold and iron salts. Neoglycoconjugates of lactose and maltose disaccharides with different linkers were used. Iron-free gold or gold-iron oxide GNPs with controlled gold-iron ratios were obtained. The average core-size diameters are in the range of 1.5-2.5 nm. The GNPs are fully characterized by (1)H NMR spectrometry, transmission electron microscopy (TEM), and UV-vis and X-ray absorption (XAS) spectroscopies. Inductive plasma-atomic emission spectrometry (ICP) and elemental analysis gave the average number of neoglycoconjugates per cluster. The magnetic properties were measured in a SQUID magnetometer. The most remarkable results was the observation of a permanent magnetism up to room temperature in the iron-free gold GNPs, that was not present in the corresponding gold-iron oxide GNPs.

Ferric Compounds↗

PEG-modified gold nanorods with a stealth character for in vivo applications.

Gold nanorods prepared in hexadecyltrimethylammonium bromide (CTAB) solution are expected to provide novel materials for photothermal therapy and photo-controlled drug delivery systems. Since gold nanorods stabilized with CTAB show strong cytotoxicity, we developed a technique to modify these with polyethyleneglycol (PEG) for medical applications. PEG-modification was achieved by adding mPEG-SH in the CTAB solution, then, excess CTAB was removed by dialysis. PEG-modified gold nanoparticles showed a nearly neutral surface, and had little cytotoxicity in vitro. Following intravenous injection into mice, 54% of injected PEG-modified gold nanoparticles were found in blood at 0.5 h after intravenous injection, whereas most of gold was detected in the liver in the case of original gold nanorods stabilized with CTAB.

Animals↗

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↗