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PubMed2002

Kinetics of radiolabelled silver uptake and depuration in the gills of rainbow trout (Oncorhynchus mykiss) and European eel (Anguilla anguilla): the influence of silver speciation.

We examined the influence of speciation on the kinetics of silver uptake and depuration in the gills of two freshwater fish, the rainbow trout (Oncorhynchus mykiss) which has high branchial Na(+) and Cl(-) uptake rates and is relatively sensitive to silver, and the European eel (Anguilla anguilla, yellow stage) which has low ion uptake rates and is relatively resistant to silver. Fish previously acclimated to the appropriate chloride level were exposed to 110mAgNO(3) (1.3 microg l(-1), sublethal) for 24 h in synthetic softwater with either low (10 microM) or high (1200 microM) chloride concentration, and then followed over a subsequent 67-day post-exposure period in silver-free water of the same chloride content. The exposures were therefore mainly to the free ion, Ag(+) in the low chloride water versus mainly to the neutral aqueous complex, AgCl(aq) in the high chloride water. In trout, but not in eel, water chloride is known to protect against physiological disturbances and toxicity caused by Ag(+). In both fish species, at both chloride levels, silver uptake exhibited complex kinetics. Gill silver loading occurred slowly until 6 h, then rose greatly to a peak at 12 h, followed by significant net depuration thereafter during continued exposure. By 24 h, net gill loading was three- to fivefold greater from AgCl(aq) than from Ag(+) exposure in both species, and threefold greater in trout than in eel under both conditions, with trout holding a lower fraction of the whole body burden in their gills. During the post-exposure period, depuration of silver from the gills occurred rapidly in trout, but very slowly in eel, such that gill silver burdens were greater in eel throughout the 67-day period on both an absolute and relative basis (e.g. 35% of whole body burden in eel versus <3% in trout at day 8). The kinetics of depuration were described by two phase exponential models, with break points between the fast and slow phases at 1 and 15 days for trout and eel, respectively. We conclude that speciation affects not only uptake rates but also the kinetics of depuration. When silver is loaded from AgCl(aq) it is clearly more labile than from Ag(+) exposures, with 1.6-1.8-fold greater loss rates during the fast phases in both species. Differences in branchial silver uptake between eel and trout correlate well with differences in acute toxicity, but are not as large as differences in ion uptake rates. The complex time-dependent patterns of gill loading, and the higher loading from AgCl(aq) than from Ag(+), mean that gill total silver burden is not an appropriate endpoint for biotic ligand modelling.

Adaptation, Physiological↗
PubMed2004

Bioavailability of silver and its relationship to ionoregulation and silver speciation across a range of salinities in the gulf toadfish (Opsanus beta).

Silver is taken up as a Na(+) analog (Ag(+)) by freshwater organisms, but little is known about its bioavailability in relation to salinity. Adult Opsanus beta were acclimated to 2.5, 5, 10, 20, 40, 60, 80, and 100% seawater (Cl(-)=545 mM) and exposed for 24 h to 2.18 microg L(-1) silver as (110m)Ag-labelled AgNO(3), a concentration close to the U.S. EPA marine criterion and less than 0.1% of the acute 96-h LC50 in seawater. Plasma osmolality, Na(+), and Cl(-) remained approximately constant from 100% down to 20-40% seawater, thereafter declining to 89% (osmolality) and 82% (Na(+), Cl(-)) of seawater values at the lowest salinity (2.5% seawater), while plasma Mg(2+) was invariant. Ionic measurements in intestinal fluids and urine supported the view that above the isosmotic point (about 32% seawater), toadfish drink the medium, absorb Na(+), Cl(-), and water across the gastrointestinal tract, actively excrete Na(+) and Cl(-) across the gills, and secrete Mg(2+) into the urine. Below this point, toadfish appear to stop drinking, actively take up Na(+) and Cl(-) at the gills, and retain ions at the kidney. Silver accumulation varied greatly with salinity, by nine-fold (whole body), 26-fold (gill tissue), and 18-fold (liver), with the maxima occurring in 2.5% seawater, the minima in 40% seawater (close to the isosmotic point), and slightly greater values at higher salinities. Highest silver concentrations occurred in liver, second highest in gills, intermediate concentrations in kidney, spleen, and gastrointestinal tissues, and lowest in swim bladder and white muscle, though patterns changed with salinity. There were substantial biliary but minimal urinary levels of silver. The salinity-dependent pattern of silver accumulation best correlated with the abundance of the neutral complex AgCl(0), though the presence of small amounts of Ag(+) at the lowest salinities may also have been important. In contrast, silver accumulation in the esophagus-stomach was greatest in 100% seawater and least at the isosmotic salinity (five-fold variation), a pattern probably explained by drinking and silver uptake into the blood through the gills. Models of silver bioavailability across salinity must consider the presence of silver-binding ligands on both gills and gastrointestinal tract, changing silver speciation, and the changing ionoregulatory physiology of the organism.

Animals↗
PubMed2005

An investigation of the surface-enhanced Raman scattering (SERS) effect from a new substrate of silver-modified silver electrode.

A roughened silver electrode modified with silver nanoparticles is used as a substrate, on which high-quality surface-enhanced Raman spectroscopy (SERS) of isonicotinic acid (INA) are obtained, indicating that the silver-modified silver electrode is a highly SERS-active substrate. It is difficult to separate the contributions of the electromagnetic and chemical mechanisms to the great enhancement of the Raman signal. The shift by 5-20 cm(-1) of the surface-enhanced Raman spectroscopy (SERS) bands and the change in their relative intensity compared with the ordinary Raman spectrum indicate the chemisorption of the sample molecules on the silver-modified silver surface. Furthermore, the silver nanoparticles modified on the roughened silver surface play the important role of magnifying the surface local electric field near the silver surface through resonant surface plasmon excitation. From the rich information on the silver-modified silver electrode obtained from high-quality potential-dependent SERS, we may deduce the adsorption behavior of INA and the probable SERS mechanism in the process. The probable reasons are given.

Electrodes↗
PubMed1988

The mechanism accounted for the silver staining "fast technique" development and its histochemical meaning: I. The correlation between the silver staining intensity and the tissue bound ferric ion and some other tissue histochemical reactivities.

The mechanism accounted to accomplish the silver staining "fast technique" on tissues sections was studied towards the correlation among histophotometric measures concerning the silver staining intensity and the intensity provided by some histochemical reactions performed on spleen and liver sections from rats and pigs. By treating previously these histological sections with thioglycolate or oxalate solutions in progressive concentrations and afterwards subjecting them to a silver staining "fast technique", it was demonstrated that the silver staining intensity decreases proportionally to the thioglycolate or the oxalate solution concentration. The regression line of the silver staining intensity on the thioglycolate or the oxalate solution concentration was established, as well as its regression coefficient. On the other hand, on histological sections previously subjected to the thioglycolate or the oxalate treatment, some histochemical techniques were performed and the histophotometric measures concerning the intensity of each histochemical technique used were taken and its regression line, as well as its regression coefficient were established. By comparing the silver staining intensity regression line (or its regression coefficient) with the regression lines established for the histochemical techniques used, it was tested the correlation between the silver staining and the reactivity of some reactive groups contained into the tissues. In this manner, the influence of such reactive groups on the silver staining development was tested. The results show that there is no correlation between the silver staining intensity and the reactivity degree of the reducing groups (-SH- and carbonyl group), the 1-2-glycolic group, as well as of some protein reactive groups (phenol, imidazole, carboxylic groups). On the other hand, taking into account the respective regression lines and its regression coefficient, the comparison between the silver staining intensity and the Prussian blue reaction intensity shows a close relationship between them. This finding suggests that for the silver staining "fast technique" the tissue bound ferric ion accomplishes a very important role and can be accounted for its mechanism and its histochemical meaning.

Animals↗
PubMed2004

Mechanism of growth of colloidal silver nanoparticles stabilized by polyvinyl pyrrolidone in gamma-irradiated silver nitrate solution.

Silver nanoparticles were prepared by using polyvinyl pyrrolidone (PVP) as a stabilizer and gamma-irradiation. Transmission electron microscopy (TEM) results showed that both the amount and the molecular weight of PVP in the irradiated solution considerably affect the average size of the silver nanoparticles. The average size of the silver nanoparticles decreases with increasing the amount of PVP in the solution, but increases with increasing its molecular weight. Further, TEM showed that the silver nanoparticles become disassembled into smaller nanoparticles after dilution with distilled water and sonication. Since the processes of dilution and sonication are not expected to result in chemical reactions or to split the silver nanoparticles, we conclude that each silver nanoparticle prepared by [Formula: see text] -irradiation consists of several smaller nanoparticles surrounded by PVP. Thus, based on these observations, we propose a three-step mechanism for the growth of the silver nanoparticles under the conditions considered here. In the first step, the silver ions interact with PVP, then in the second step the silver ions that are exposed to gamma-irradiation are reduced to silver atoms; nearby silver atoms then aggregate at close range. These aggregates are the primary nanoparticles. Finally, these primary nanoparticles coalesce with other nearby primary nanoparticles or interact with PVP to form larger aggregates which are the secondary (final) nanoparticles.

Journal Article↗
PubMed1997

Elimination study of silver in a hemodialyzed burn patient treated with silver sulfadiazine cream.

Silver sulfadiazine (SSD) cream is a potent agent for the treatment of burns. In a patient with end-stage renal disease, we observed a marked elevation in serum silver concentration in the course of 2 weeks of SSD cream therapy (200 g/d). Serum concentration of silver reached a maximum of 291 ng/mL in association with a rapid deterioration of mental status. SSD therapy was discontinued, and hemodialysis, hemofiltration, or plasma exchange was continually performed. Four months later, the patient died. At autopsy, profoundly elevated levels of silver were found in brain tissues of this patient (617.3, 823.7 ng/g wet tissue weight in the cerebrum and cerebellum, respectively). To determine the most efficient therapy to remove silver from serum, we compared hemodialysis (HD), hemofiltration (HF), and plasma exchange (PE). Both plasma exchange and hemofiltration were effective in decreasing serum silver, and their effects were additive. By contrast, HD was ineffective in reducing serum silver. This case illustrates that, on SSD cream therapy, burn patients with disturbed renal function are at risk of accumulating silver in serum and tissue to the level that may cause neuralgic decompensation. Removal of serum silver can best be effected by PE, particularly when combined with HF. In contrast, HD per se does not appear efficacious. None of these blood purification modalities improves deterioration of neurological status potentially attributable to silver deposition in brain tissues.

Adult↗
PubMed2003

Evidence of the production of silver nanoparticles via pretreatment of Phoma sp.3.2883 with silver nitrate.

AIMS: The objective was to demonstrate the size of silver particles produced by the filamentous fungus Phoma sp.3.2883 via adsorption and accumulation, and to confirm that this silver was in a reduced state. METHODS AND RESULTS: Mycelium was freeze-dried and then shake-cultured in a silver nitrate solution. It was found that up to 13.4 mg of silver was produced per gram of dry mycelium via atomic absorption spectrometer (AAS) analysis. The silver particles adsorbed on the mycelium were observed and measured under transmission electron microscope and their estimated size was 71.06 +/- 3.46 nm. Further examination of the particles via X-ray photoelectron spectroscope confirmed that the adsorbed silver particle had been reduced. CONCLUSION: The frozen mycelium of Phoma sp3.2883 has the potential for use in silver nanoparticle production. SIGNIFICANCE AND IMPACT OF THE STUDY: Silver nanoparticles could be used in the oil industry as an important catalyst and in the field of human medicine as a bactericide. The fungus Phoma sp3.2883 is a potential biosorbent that could be used for the production of these silver nanoparticles, and may also be useful in waste detoxification and in silver recovery programmes.

Adsorption↗
PubMed1994

Organ distribution of silver and the effect of silver on copper status in rats.

Tissue distribution of silver, alteration in tissue concentration of copper, zinc and iron, as well as changes in serum ceruloplasmin (CP) status were investigated in Fischer 344 rats after intraperitoneal (i.p.) administration of silver (9.3 mumol Ag/kg body wt.) as silver nitrate alone or combined with zinc (46.5 mumol Zn/kg) as zinc sulfate once a day for six successive days. Silver deposited in all the tissues examined, particularly in the pancreas, showing silver concentration in the serum, kidney, heart and lung to be significantly increased by simultaneous injection of zinc, while zinc concentration in the liver, pancreas and heart was significantly affected by silver. The most prominent effect of silver administration was observed in the copper status. As the result of altered copper metabolism by silver administration, copper concentration in the liver, pancreas and kidney was significantly changed, and serum copper concentration and CP oxidase activity were decreased to 60% and 25% of the control value, respectively. However, immunoblot analysis of serum CP in silver-treated groups showed only a slight decrease in protein levels, suggesting that most of the CP existed as an oxidase inactive apo-form. Simultaneously administered zinc hardly affected such changes. These results indicate that silver administration causes a disturbance of copper metabolism, and that zinc hardly plays a protective role against such changes.

Animals↗
PubMed2002

Surface-enhanced Raman spectroscopy study on the structure changes of 4-mercaptopyridine adsorbed on silver substrates and silver colloids.

Surface-enhanced Raman scattering (SERS) of 4-mercaptopyridine (4-mpy) adsorbed on HNO3 etched silver foil, chemically deposited silver films (silver mirror) and silver colloids were measured. The SERS study has revealed that 4-mpy was adsorbed onto the three kinds of silver surfaces by a sulfur-silver bond with the plane of pyridine ring being normal to the silver substrates. The structure of 4-mpy adsorbed on the silver surfaces depends largely on the pH values of environment. When the pH values of the environment are changed, the structure of 4-mpy adsorbed on silver surfaces can easily be altered through a protonation or deprotonation reaction occurring on the N atom of the pyridine ring, and the modified structure shows unique characters on the SERS spectrum. Owing to the remarkable enhancement ability of SERS technique and characteristic spectrum of different species, a monolayer of 4-mpy assembled on a silver mirror holds potential as a H+ sensor for highly sensitive detection of the proton concentration in an aqueous solution.

Adsorption↗
PubMed2006

Direct synthesis of nanocrystalline silver from the reaction between silver carboxylates and n-trioctylphosphine.

Neat n-Trioctylphosphine (TOP) has been used for the first ever time for reduction of silver nitrate and silver carboxylates (citrate, oleate, and myristate) under mild thermal reaction conditions. UV-visible absorption measurements of re-dispersible silver particles that were obtained by reduction of silver myristrate (product-IV) and silver nitrate (product-I) showed surface plasmon resonance absorption peak at 400 nm. The powder XRD pattern of fcc zero-valent silver resulted in diameters in the range of about 25-30 nm. TEM analysis showed particle diameter similar to that was observed by the XRD. FTIR spectroscopy revealed that the organics from the carboxylate group are retained by the nano-particles in case of product-IV however, presence of TOP is observed in product-I. It is found that when silver nitrate is reduced by TOP, spherical silver nano-particles with poor redispersity are formed but extended heating results in formation of long silver rods of micrometer size however, the re-dispersible nano-particles are easily formed when silver carboxylates are reduced by TOP.

Carboxylic Acids↗
PubMed2005

Novel silver nanostructures from silver mirror reaction on reactive substrates.

Novel silver clusters have been prepared by simply carrying out the silver mirror reaction on certain reactive substrates. Leaflike fractal silver microstructures and perpendicularly aligned silver nanosheets were produced on a commercially available copper foil and sandpaper-rubbed copper foil, respectively. The surface features of copper foils and the chemical state of Cu atoms play important roles in regulating the morphological structures of the resulting silver clusters. Silver nanoclusters with various morphologies ranging from the leaflike to flowerlike hierarchical structures can be produced from the silver mirror reaction on commercially available copper foils after being treated with a dilute aqueous HCl solution under different conditions. The aqueous solution of silver nanosheets shows an optical absorption spectrum with a broad light-scattering peak at about 350 nm, compared to a corresponding surface plasmon absorption band around 430 nm for silver nanoparticles from the conventional silver mirror reaction on glass.

Journal Article↗
PubMed2001

Chronic effects of silver exposure on ion levels, survival, and silver distribution within developing rainbow trout (Oncorhynchus mykiss) embryos.

Rainbow trout embryos were chronically exposed to silver (as AgNO3) in moderately hard water (120 mg CaCO3/L, 0.70 mM Cl-, 1.3 mg/L dissolved organic matter. 12.3+/-0.1 degrees C) at nominal concentrations of 0.1, 1, and 10 microg/L (measured = 0.117+/-0.008, 1.22+/-0.16, and 13.51+/-1.58 microg/L, respectively) to investigate the effects on mortality, ionoregulation, and silver uptake and distribution of the embryo. Mortalities in the low concentrations (0.1 and 1.2 microg/L) were not significantly different from controls throughout embryonic development (days 1-32 postfertilization). Mortalities of embryos in the 13.5-microg/L treatment reached 56% by day 32 postfertilization (33% when accounting for control mortality), by which time more than 50% of surviving embryos had hatched. Accumulation of silver in whole embryos of 1.2- and 13.5-microg/L treatments reached the highest concentrations of 0.13 and 0.24 microg/g total silver, respectively, by day 32, but whole embryo silver burden was not correlated with mortality. Silver concentrations in different compartments of the whole embryo (chorion, dissected embryo, and yolk) were greatest just before hatch and were higher in the chorion for all experimental treatments. Up to 85% of total whole embryo silver content was bound to the chorion, which acts as a protective barrier during silver exposure. Whole embryo Na+ concentration in the 13.5-microg/L treatment was significantly reduced relative to controls from days 23 to 32 postfertilization, and levels in the embryo were reduced by 40% at day 32 postfertilization, indicating that silver toxicity in the whole embryo is associated with an ion regulatory disturbance that is similar to the acute effect of AgNO3 in juvenile and adult trout.

Animals↗
PubMed1995

Multi-nuclear and multi-dimensional nuclear magnetic resonance investigation of silver iodide-silver phosphate fast ion conducting glasses.

The results of a multi-nuclear nuclear magnetic resonance (NMR) study of (AgI)x(Ag2O)y(P2O5)1-x-y glasses are reported. Using the two-dimensional variable-angle correlation spectroscopy experiment, the isotropic and anisotropic chemical shift interactions of phosphorus were determined as a function of silver iodide and silver oxide composition. From these measurements we determine the average conformation of the phosphate groups. In addition, the 109Ag NMR spectra were recorded, as a function of both composition and temperature. At high silver oxide concentrations, interaction between the silver and phosphate groups has been detected, but in glasses in the series the (AgPO3)x(AgI)1-x 31P NMR is strikingly independent on the silver iodide composition. The temperature dependence of the silver NMR linewidths in these systems shows clearly the silver mobility, and at lower temperatures no evidence for multiple distinct silver binding sites was observed. The silver chemical shift is strongly dependent on both composition and temperature. The former effect is interpreted in terms of the influence on the chemical shift of binding to oxygen versus iodine.

Anisotropy↗
PubMed2006

Surface-enhanced Raman scattering system of sample molecules in silver-modified silver film.

Surface-enhanced Raman scattering (SERS) spectrum of very good quality of "silver nano-particles/sample molecules/silver film" system was reported by nesting the sample molecules to the gap of silver nano-particles and silver film, indicating that "silver nano-particles/sample molecules/silver film" is a highly SERS-active system. Not only was the number of the vibrational modes increased, but also were the frequencies of Raman bands up and down shifted. It is difficult to separate the contributions of the electromagnetic and chemical mechanisms to the great enhancement of the Raman signal. The shift by 5-30cm(-1) of the SERS bands and the change in their relative intensity compared with the ordinary Raman spectrum indicate the chemisorption of the sample molecules on the silver-modified silver surface. Furthermore, the silver nano-particles modified on the rough silver film surface play an important role in magnifying the surface local electric field near the silver surface through resonant surface plasmon excitation. From the rich information, obtained from high-quality SERS of PHBA in ternary system, we inferred that PHBA molecules in ternary system adsorb onto the metal surfaces through carboxyl at a perpendicular orientation.

Hydroxybenzoates↗
PubMed2000

A historical review of the use of silver in the treatment of burns. II. Renewed interest for silver.

In 1965, Moyer revived interest in silver nitrate solution. He concluded on the basis on in vitro and in vivo studies that a 0.5% solution represented the lowest concentration at which antibacterial action (against Staphylococcus aureus, haemolytic streptococci and generally against Pseudomonas aeruginosa and E. coli) was obtained. Mafenide acetate was introduced a short time after the reintroduction of silver nitrate, followed a few years later by silver sulphadiazine. Thus, in a short period of time three medicaments appeared on the market which represented a radical change in the topical treatment of burns. The action of silver sulphadiazine has been intensively studied. Since silver sulphadiazine does not offer sufficient protection to prevent or retard the growth of gram-negative bacteria in patients with burns covering more than 50% of body surface, Monafo introduced the combined preparation silver sulphadiazine and cerium nitrate. Although various attempts have been made to develop more effective silver compounds, so far silver sulphadiazine still remains the most widely used substance of this type.

Anti-Infective Agents, Local↗
PubMed1979

Factors affecting the formation of metallic silver and the binding of silver ions by tissue components.

The rate of formation of metallic silver has a maximum when plotted as a function of pH. The site of this maximum on a pH scale differs noticeably for various tissue elements. By contrast, the amount of silver ions bound to the tissue is a monotonously increasing function of the pH. A temperature rise decreases the length of the induction period and increases the gradient of the ascending section of the kinetic curve representing the formation of metallic silver. It also increases the maximum amount of silver ions bound to the tissue. An increase in the concentration (activity) of the silver ions in the impregnating bath has the same effect. Chemical composition and concentration of the complexing agent, as well as "special" ions in the impregnating bath to which earlier some definitive role has been attributed in the silver staining methods, proved to be ineffective when both pH and activity of silver ions were kept constant. Illumination of the reaction was also ineffective. The kinetic curves obtained in nonaqueous but polar media (e.g., acetone) exhibited the same qualitative characteristics as those obtained in aqueous solutions. No reaction between silver ions and tissue was observed in apolar solvents.

Histocytochemistry↗
PubMed1983

Acute toxicity of some silver salts of sulfonamides in mice and the efficacy of penicillamine in silver.

The silver salt of 2-metanilamido-5-chloropyrimidine (AgMCP) and the sodium, amminosilver and trimethylphosphite-silver salts of 3',5'-dichlorobenzenesulfonanilide (NaDBS, AgNH3DBS and AgP(OCH3)3DBS were synthesized as possible antibiotic of antiparasitic drugs. All the organosilver compounds were extremely water-insoluble. For animal studies these, and other reference compounds, were given as fine suspensions in an Emulphor-safflower oil mixture. The ip LD50's in mice in mmol/kg were: 1.67 for NaDBS, 0.22 for silver acetate (AgAc), 0.15 for AgP(OCH3)3DBS, 0.13 for AgMCP and 0.10 for AgNH3DBS. When given by mouth, 15 mmol AgAc/kg produced a high mortality, but none of the organosilver compounds caused death in maximal doses (1.9 to 2.6 mmol/kg) that could be given based on considerations of total volume and stability of the suspension. All the silver compounds, including AgAc, produced a similar toxic syndrome with initial hyperexcitability, ataxia, central nervous depression, labored breathing, loss of righting reflex and death. Most deaths occurred between 12 and 24 hours after dosing. In contrast, animals given NaDBS often died within 3 hours although the major signs were very similar to those produced by the silver compounds. When given ip as a single dose 30 minutes after AgAc, D-penicillamine was effective in reducing mortality, but it had no effect on the mortality of the organosilver compounds. Histological studies revealed similar patterns of silver deposition, especially in the liver and kidneys, at 6, 18 and 24 hours after the organosilver compounds and after AgAc. We conclude that the presence of silver contributes significantly to the acute toxicity of these sulfonamides although they may dissociate free silver less readily than does AgAc.

Animals↗