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PubMed1979

Argyria: clinical implications of exposure to silver nitrate and silver oxide.

This article reports the clinical findings in a work force of 30 individuals who were exposed to silver nitrate and silver oxide. Six individuals had argyria and 20 had argyrosis (deposition of silver in the eye). Measurements of blood silver levels were included as part of the examination. The results of this examination generally support the benign nature of argyria, although the question of silver causing a decrement in kidney function and night vision is not settled. Periodic slit lamp examinations as well as monitoring of silver air concentrations are necessary to assure that engineering controls are actually limiting worker exposure to silver.

Adult↗
PubMed2002

Silver staining of proteins on electroblotting membranes and intensification of silver staining of proteins separated by polyacrylamide gel electrophoresis.

A fast and convenient method for silver staining of proteins on electroblotting membranes was developed based on Gallyas' histochemical intensifier and applied to human endothelial cell proteins separated by one- and two-dimensional electrophoresis and electroblotted to polyvinyl difluoride membranes. The method allowed detection of proteins on membranes with a sensitivity equal to the sensitivity of the most sensitive silver-staining protocols for electrophoresis gels. Also, the method was compatible with preceding immunostaining on the same membrane. Furthermore, an intensifying method for proteins in silver-stained SDS-PAGE gels was developed based on Gallyas' histochemical intensifier. This method was applied to proteins separated by one- and two-dimensional gel electrophoresis and visualized by one of several silver-staining methods. Maximal intensification was achieved for the less sensitive but fast acidic silver-staining protocols, but even for the very sensitive alkaline protocols a significant increase in signal to noise ratio was obtained. In particular, negatively stained or invisible proteins on the silver-stained gels were found to be visualized by the Gallyas stain. Proteins from silver-stained and Gallyas-stained gels were identified by mass spectrometry, and the intensification procedure was fully compatible with mass spectrometry.

Cell Line↗
PubMed1979

Kinetics of formation of metallic silver and binding of silver ions by tissue components.

The effect of time on the formation of metallic silver by tissue reducing groups follows a curve which can be divided into three main parts. In the first, which may last for several hours, the reaction is very slow, and only an undetectably small amount of metallic silver is produced. In the second period the speed of the reaction first increases in a progressive manner and then begins to decrease gradually; during the third period the speed approaches zero asymptotically. Binding of the silver ions by the tissue commences initially at its fastest rate; the level then decreases steadily to zero within about a quarter of an hour. There is no direct relationship between the amount of silver ion bound to the tissue and the formation of metallic silver. The latter cannot take place by way of direct (non-catalysed) reaction. The following mechanism is proposed for the process: Transfer of electrons from the reducing molecules to the silver ions is mediated at first by certain tissue sites (catalytic points) and then also by the steadily increasing total surface area of the metallic silver grains (autocatalysis). On the basis of this mechanism, several anomalies of both the argentaffin and argyrophil reactions are explained.

Histocytochemistry↗
PubMed1999

Determination of the silver ion release from polyurethanes enriched with silver.

The Erlanger silver catheter was developed in order to reduce the risk of infection from long-term catheters by means of silver ions, which are known to have antibacterial properties. This is achieved by incorporating silver into polyurethane catheters by means of a special procedure. The aim of this materials science study was to verify the release of silver ions from the polyurethanes. Static experiments were carried out following the usual norms. Clinically relevant dynamic experiments, which were designed and constructed at this institute, were also performed. The eluates from both experiments were analyzed by anodic stripping voltammetry. Polyurethanes filled with silver, as used in the Erlanger silver catheter, release silver in static as well as in dynamic experiments. If the experimentally determined releases are converted to the usual catheter length of 30 cm, the release is about 0.1 microgram/l. This lies in the order of concentrations that have been reported in the literature to be antibacterial.

Catheterization↗
PubMed1994

Linking radiosilver to monoclonal antibodies reduced by ascorbic acid. Comparison of results with stable silver using gravimetric technique and silver 110-M using radiotracer technique.

Radiosilver-111 and Radiogold-199 were proposed by us (1) as suitable isotopes for radioimmunotherapy in areas such as India by reason of their suitable half-lives and B-emissions (Ag-111 T1/2 = 7.45 d and Au-199 T1/2 = 3.15 d). Since silver is monovalent, it is difficult to link to conventional bifunctional chelates. We therefore explored the use of sulfur-based linkers (2). Encouraged by the Thakur and De Fulvio Technique (3) of linking technetium to disulfide groups in antibodies reduced by ascorbic acid that is eminently biocompatible, we have explored the linkage of silver to immunoglobulin reduced by ascorbic acid. The linkage of silver was assessed with stable Ag-108 using dialysis to quantify the free silver after the reaction of silver and reduced immunoglobulins in various molar ratios (1:1, 1:2, 1:5, 1:10). The silver quantity was estimated gravimetrically after precipitation as chloride. It was observed that using these molar ratios there was negligible silver efflux into the dialysate, suggesting stable linkage. We also assessed the linkage using Ag-110M as radiotracer. The comparative results with the two techniques are described.

Antibodies, Monoclonal↗
PubMed1994

How to detect gold, silver and mercury in human brain and other tissues by autometallographic silver amplification.

Gold, silver, mercury and zinc bind chemically to sulphide or selenide ions and create crystal lattices that can be detected in histological sections by a silver amplification technique called autometallography (AMG). The technique specifically magnifies such nanometer-sized catalytic crystals. For each metal, a detailed protocol has been worked out. If several different AMG metals/metal molecules are present in the same tissue, it is possible to distinguish one from another. The AMG technique is based on the capability of small crystal lattices of the aforementioned metals and metal molecules to initiate AMG silver amplification. Electrons released from adhering hydroquinone molecules reduce silver ions that are integrally connected with the crystal lattices. In this manner, particles consisting of only a few atoms of, say, gold, or molecules of mercury selenide (Figure 1), can be silver amplified to a size at which they can be detected in the electron microscope, or even further to dimensions that can be observed in the light microscope. Thus the AMG technique opens up the possibility of visualizing gold, e.g. in the nervous system of rheumatic patients who have been treated with aurothiomalate. Mercury can similarly be visualized in tissues from individuals who have been exposed to mercury, either through leaching from amalgam dental fillings, through eating fish, or by occupational exposure, and silver in the central (CNS) and peripheral nervous systems (PNS) and other tissues from individuals exposed to silver in one form or another. In the future, the possibility of demonstrating vesicular zinc, a particular pool of endogenous zinc that is found in terminals of zinc-enriched neurons (ZEN neurons), might prove valuable for pathological interpretation of diseases such as Alzheimer's disease. The vesicular zinc, present in some of the synaptic vesicles of ZEN neuron terminals, is most impressively demonstrated by AMG in telencephalic structures. It is becoming increasingly indisputable that vesicular zinc is related to synaptic activity influencing or modulating facilitatory synapses. ZEN neurons are probably a sub-population of glutaminergic neurons. A technique for the post-mortem demonstration of vesicular zinc in terminals of ZEN neurons in human brains is therefore urgently required.

Animals↗
PubMed1997

Murine silver-induced autoimmunity: silver shares induction of antinucleolar antibodies with mercury, but causes less activation of the immune system.

BACKGROUND: Mercury and silver induce antinucleolar autoantibodies (ANoA) targeting the 34-kDa nucleolar protein fibrillarin in susceptible mouse strains. Mercury has the ability to cause a general activation of the immune system, but antigen-specific mechanisms following direct or indirect interaction between mercury and fibrillarin are now believed to play a crucial role in the autoimmune pathogenesis. Our previous studies showed that silver neither induced the systemic immune complex deposits nor the increase of serum immunoglobulins seen after mercury treatment. The main objective of this study was to examine the relation between activation of the immune system and the induction of ANoA. METHODS: During 4 weeks of subcutaneous silver nitrate injections into mice of the susceptible A.SW and SJL strains and the resistant A.TL strain, the number of T and B cells as well as the expression of cell surface activation and proliferation markers were monitored by flow cytometry. The number of cytoplasmic Ig+ splenocytes was determined by direct immunofluorescence technique on slides, and serum Ig levels as well as anti-ssDNA anti anti-DNP antibodies were determined by ELISA. Serum ANoA were monitored by the indirect immunofluorescence technique. RESULTS: Silver caused in the susceptible strains a weaker and later activation and proliferation of T and B cells than mercury, and no significant polyclonal B cell activation. In contrast, the ANoA titer was not different from that seen in mercury-treated mice of the same strains. Silver-treated mice of the A.TL strain showed neither activation of the immune system nor ANoA. CONCLUSIONS: Despite being as effective as mercury inducing ANoA, silver caused only a slight activation of the immune system. This demonstrates that the massive activation of the immune system in mercury treatment is not necessary for the induction of ANoA, and indicates that (auto)antigen-specific mechanisms are likely to play a key role in mercury- and silver-induced murine autoimmunity.

Animals↗
PubMed2002

Use of dicyclohexano-18-crown-6 to separate traces of silver(I) from potassium thiocyanate in hydrochloric acid media, and determination of the silver by atomic absorption spectrometry.

Solvent extraction with 0.05 mol L(-1) dicyclohexano-18-crown-6 (DC18C6) in 1,2-dichloroethane, coupled with flame atomic absorption spectrometry (AAS), has been investigated as a new method for separation of trace amounts of silver(I) from 0.05 mol L(-1) potassium thiocyanate in 1.0 mol L(-1) hydrochloric acid media and quantification of the amount of silver present. The method is based on the formation of an extractable ion-association product, [DC18C6.K](+)[Ag(SCN)(2)](-), with a metal-to-crown ether ratio of 1:1 (as derived from slope analysis data). Stripping of the extracted silver(I) in the 1,2-dichloroethane phase was achieved within 5 min by use of 3.0 mol L(-1) potassium thiocyanate. Reducing the concentration of acid in the sample solution to 0.1 mol L(-1) improved the preconcentration factor severalfold. Excellent tolerance of the proposed method to the presence of foreign ions in solution with silver(I) was demonstrated. A detection limit of 13 ng mL(-1) was derived from the mean value of the blank plus three times its standard deviation. The method was used to determine traces of silver(I) after separation from gold(III), platinum(IV), and palladium(II) matrices on the basis of extractability differences with 18-membered crown ethers under specified conditions. The efficiency of the adopted ion-association mechanism for silver(I) extraction was apparent from the average recovery of 96% for spiked standards by use of the back-washing technique. The proposed extraction procedure was applied to the determination of traces of silver(I) in a selection of chemical reagents.

Journal Article↗
PubMed2005

Coordination networks with flexible ligands based on silver(I) salts: complexes of 1,3-bis(phenylthio)propane with silver(I) salts of PF6-, CF3COO-, CF3CF2COO-, CF3CF2)CF2COO-, p-TsO-, and CF3SO3-.

The synthesis and characterization of nine coordination networks based on 1,3-bis(phenylthio)propane, L(3), and silver(I) salts of PF(6)(-) (1), CF(3)COO(-) (2), CF(3)CF(2)COO(-) (3), CF(3)CF(2)CF(2)COO(-) (4), p-TsO(-) (5, 6), and CF(3)SO(3)(-) (7-9) are reported. Only 1 and other "isostructural" complexes with weakly coordinating anions such as ClO(4)(-) and SbF(6)(-) are of the host-guest type. In all the other complexes, the anions and the acetone molecules, when present, are coordinated to the metal. Most of the complexes studied here form a 2D-coordination network. Only 4 and 5 adopt a polymer-like chain structure. The packing of the chains of 4 is pseudohexagonal compact, while that of 5 is of the centered type. In complex 1, the silver atom is tetrahedrally coordinated to the sulfur atoms of four different ligands. The PF(6)(-) anions and acetone molecules, sandwiched between silver-ligand cationic sheets, are held through van der Waals interactions. In each of the three perfluorocarboxylates (2-4), two silver atoms are joined by the anions in a diatomic bridging mode. The Ag...Ag distances are sufficiently short to indicate weak metal...metal interactions. The dimeric units in 2 and 3 are interconnected through the ligands, thereby generating a 2D-network of neutral sheets, while, in 4, the dimeric units are bound to four ligands and a 1D-coordination polymer is generated. In the case of the sulfonate anions (p-TsO(-) and CF(3)SO(3)(-)), the crystallization solvent influences the structure adopted. Thus, in 5, 7, and 9 obtained from petroleum ether, or other nonpolar solvents, two silver atoms are bound in a double-bridge fashion, while a monobridge mode is noted for 6 and 8, both recrystallized from diethyl ether. In 8, both bridging types are observed. The thermogravimetric investigation, in the room temperature-450 degrees C interval, of complexes 1, 3, and 7, which incorporate acetone molecules in their crystal structures, reveals a two-step weight loss for 1 (the acetone molecules are lost first followed by the ligands, leaving behind the silver salt), while complexes 3 and 7 decompose in a single step to metallic silver.

Journal Article↗
PubMed2005

Hydrothermal-induced assembly of colloidal silver spheres into various nanoparticles on the basis of HTAB-modified silver mirror reaction.

Small colloidal silver spheres (diameter < 10 nm) were found to assemble into various silver nanoparticles including cubes, triangles, wires, and rods in water in the presence of HTAB (n-hexadecyltrimethylammonium bromide) at 120 degrees C, while the colloids were generated in situ on the basis of a HTAB-modified silver mirror reaction during the synthesis process. Adjustment of the synthesis parameters, in particular the concentrations of HTAB and [Ag(NH3)2]+, led to an obvious shape evolution of silver nanoparticles, thus resulting in the shape-selective formation of the silver nanoparticles. The monodisperse nanocubes with a well-defined crystallographical structure (a single crystal bounded by six {200} facets) have a strong tendency to assemble into two-dimensional arrays on substrates. The nanowires with uniform diameter usually existed in the form of two-dimensional alignments. The findings suggested that hydrothermal-induced assembly of small silver colloidal particles should be a convenient and effective approach to the preparation of various silver nanoparticles.

Journal Article↗
PubMed1991

Ultrastructural localization of silver in rat testis and organ distribution of radioactive silver in the rat.

The deposition of silver after a single intravenous injection (2 micrograms Ag g-1 body weight) was studied in the testes of Wistar rats 24 h and 1 and 2 weeks after dosing with radiolabelled 110AgNo3 (2 micrograms Ag and 1.2 kBq g-1 body weight). Also, the temporal accumulation of silver during the experimental period was monitored in the blood, testes, epididymides, kidney, liver and brain. The subcellular distribution of silver within the testes was demonstrated by using the histochemical technique of autometallography. Silver was cleared rapidly from the blood. After an initial rise, concentrations in organs remained almost stable throughout the experimental period. Silver was especially abundant in interstitial macrophages and in the basement membrane. Deposits of silver were found in all cell types of spermatogenesis and in the lysosomes of the Sertoli cells.

Animals↗
PubMedDate not supplied

Autometallographic detection of silver in hypothalamic neurons of rats exposed to silver nitrate.

The silver amplification technique, autometallography, has been used to reveal silver accumulation in neurons in the hypothalamus of male Wistar-Kyoto rats. Silver penetrated the blood-brain barrier after exposure to silver nitrate, and differences in staining intensity were found between the hypothalamic nuclei. When using light microscopy, the silver staining of the hypothalamic neurons was highly heterogeneous. Silver was detected exclusively in lysosomes of the loaded neurons. Aspects of this heterogeneous localization are discussed in relation to the distribution of autometallographically developed gold and mercury.

Animals↗
PubMed1995

Spectrophotometric quantitation of silver in X-ray film images and silver-stained electrophoresis gel bands.

This paper describes a novel spectrophotometric method for quantitating the silver in silver-stained electrophoresis gel bands and X-ray film images. Silver in excised areas is quantitated by (i) oxidation/solubilization of Ag0 to Ag+ with nitric acid, (ii) neutralization followed by extraction into an organic solution of dithizone (diphenylthiocarbazone), and (iii) visible absorbance measurement at 600 nm. Spectrophotometric quantitation is possible because dithizone undergoes a dramatic color change from blue-green to yellow upon binding Ag+ (delta epsilon 600 = 3.28 x 10(4) M-1 cm-1). Experiments with silver-stained gels and with X-ray film images obtained by chemiluminescence and autoradiography demonstrated that the color change relates to the amount of silver present and hence to the amount of material represented by the band or image. This method is a convenient, inexpensive alternative to the use of a densitometer to quantitate silver-containing images.

Electrophoresis, Polyacrylamide Gel↗
PubMed2006

Direct synthesis and bonding origins of monolayer-protected silver nanocrystals from silver nitrate through in situ ligand exchange.

In this study, we attempt to present a direct synthesis of narrowly dispersed silver nanoparticles in a highly concentrated organic phase (>2 M) without the use of a size-selection process. The fully organic phase system contains silver nitrate as a silver precursor, n-butylamine as a medium dissolving the silver salt, dodecanoic acid as a capping molecule, toluene as a medium, and NaBH4 as a reducing reagent. Even using only generic chemicals, monodisperse silver nanocrystals with a size of 7 nm were easily synthesized on the 100-g scale in a 1-L reactor. In addition, systematic studies revealed that the silver nanocrystals synthesized through in situ ligand exchange were stabilized through bidentate bridging of carboxyl groups in dodecanoic acid.

Adsorption↗
PubMed2003

Bacterial silver resistance: molecular biology and uses and misuses of silver compounds.

Resistance to silver compounds as determined by bacterial plasmids and genes has been defined by molecular genetics. Silver resistance conferred by the Salmonella plasmid pMGH100 involves nine genes in three transcription units. A sensor/responder (SilRS) two-component transcriptional regulatory system governs synthesis of a periplasmic Ag(I)-binding protein (SilE) and two efflux pumps (a P-type ATPase (SilP) plus a three-protein chemiosmotic RND Ag(I)/H+ exchange system (SilCBA)). The same genes were identified on five of 19 additional IncH incompatibility class plasmids but thus far not on other plasmids. Of 70 random enteric isolates from a local hospital, isolates from catheters and other Ag-exposed sites, and total genomes of enteric bacteria, 10 have recognizable sil genes. The centrally located six genes are found and functional in the chromosome of Escherichia coli K-12, and also occur on the genome of E. coli O157:H7. The use of molecular epidemiological tools will establish the range and diversity of such resistance systems in clinical and non-clinical sources. Silver compounds are used widely as effective antimicrobial agents to combat pathogens (bacteria, viruses and eukaryotic microorganisms) in the clinic and for public health hygiene. Silver cations (Ag+) are microcidal at low concentrations and used to treat burns, wounds and ulcers. Ag is used to coat catheters to retard microbial biofilm development. Ag is used in hygiene products including face creams, "alternative medicine" health supplements, supermarket products for washing vegetables, and water filtration cartridges. Ag is generally without adverse effects for humans, and argyria (irreversible discoloration of the skin resulting from subepithelial silver deposits) is rare and mostly of cosmetic concern.

Drug Resistance, Bacterial↗
PubMed1999

Catheter-associated infections in urology: possible use of silver-impregnated catheters and the Erlanger silver catheter.

Indwelling urinary catheters play a very important part in urology. However, their use is accompanied by a considerable increase in the risk of nosocomial urinary tract infections. The pathophysiological cause is ascribed to pathogens that adhere to the catheter surface, proliferate and produce a biofilm. In addition to aseptic techniques, modification of the catheter material to confer antimicrobial activity plays an essential part in the prevention of catheter-related urinary tract infections. The antimicrobial efficacy of silver against gram-positive and gram-negative bacteria is well known and amply shown in vitro. The efficacy of silver-impregnated catheters is critically dependent on both the chemical structure of the incorporated silver and the way the silver has been combined with the basic catheter material. Hence, clinical studies on silver-modified catheters have so far given inconsistent results. The new technology of the Erlanger silver catheter offers the opportunity of an effective reduction in catheter-related infections.

Anti-Bacterial Agents↗
PubMed1982

Electron-microscopic observation on silver deposition in burn wounds treated with silver sulphadiazine cream.

The absorption and distribution of silver has been studied in 8 burned patients treated with silver sulphadiazine cream by electron-microscopic examination. Biopsies were taken from the burn wounds and from epithelized areas surrounding wounds. Only 1 to 2 patients treated for 12 days was observed to have silver deposits in the cytoplasm of both the epidermal cells and sweat glands. The silver deposits appeared as roughly round and oval bodies of varied size. The results indicated that very little of the silver moiety in silver sulphadiazine cream penetrated the body through the wound.

Administration, Topical↗
PubMed2004

Synthesis and structural characterization of silver(I), aluminium(III) and cobalt(II) complexes with 4-isopropyltropolone (hinokitiol) showing noteworthy biological activities. Action of silver(I)-oxygen bonding complexes on the antimicrobial activities.

Through two unequivalent oxygen donor atoms of the hinokitiol (Hhino; C10H12O2; 4-isopropyltropolone) ligand that showed noteworthy biological activities, the dimeric, silver(I)-oxygen bonding complex [Ag(hino)]2 1, the monomeric aluminium(III) complex [Al(hino)3].0.5H2O 4 and the cobalt(II) complex "[Co(hino)2]2.H2O" 6 were synthesized and characterized with elemental analysis, thermogravimetric and differential thermal analysis (TG/DTA), FTIR and solution (1H and 13C) NMR spectroscopy. The crystal structure of 1 was determined by Rietveld analysis based on X-ray powder diffraction (XPD) data and those of [Al(hino)3].MeOH 4a and [Co(hino)2(EtOH)]2 6a, being obtained as yellow block crystals and red platelet crystals, respectively, by crystallization of 4 and 6, were determined by single-crystal X-ray analysis. The antimicrobial activities of 1, 4 and 6, evaluated with minimum inhibitory concentration (MIC; microg ml(-1)), were compared with those of other metal complexes (M=Na, Li, Cs, Ca, V, Zn) with the hino- ligand. The antimicrobial activities observed in the alkali-metal salts strongly suggested that they were attributed to the effect of the anionic hino- species. The antimicrobial activities of 1 were significantly enhanced, whereas those of other metal complexes were suppressed, compared with those of the neutral Hhino and anionic hino- molecules. The antimicrobial activities observed in 1 were comparable with those of other recently found silver(I)-oxygen bonding complexes, the ligands of which had no activity. Thus, it is proposed that the antimicrobial activities of the silver(I)-oxygen bonding complexes are due to a direct interaction or complexation of the silver(I) ion with biological ligands such as protein, enzyme and membrane, and the coordinating ligands of the silver(I) complexes play the role of a carrier of the silver(I) ion to the biological system.

Aluminum↗