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Dynamics of microcystins-LR and -RR in the phytoplanktivorous silver carp in a sub-chronic toxicity experiment.

A sub-chronic toxicity experiment was conducted to examine tissue distribution and depuration of two microcystins (microcystin-LR and microcystin -RR) in the phytoplanktivorous filter-feeding silver carp during a course of 80 days. Two large tanks (A, B) were used, and in Tank A, the fish were fed naturally with fresh Microcystis viridis cells (collected from a eutrophic pond) throughout the experiment, while in Tank B, the food of the fish were M. viridis cells for the first 40 days and then changed to artificial carp feed. High Performance Liquid Chromatography (HPLC) was used to measure MC-LR and MC-RR in the M. viridis cells, the seston, and the intestine, blood, liver and muscle tissue of silver carp at an interval of 20 days. MC-RR and MC-LR in the collected Microcystis cells varied between 268-580 and 110-292 microg g(-1) DW, respectively. In Tank A, MC-RR and MC-LR varied between 41.5-99.5 and 6.9-15.8 microg g(-1) DW in the seston, respectively. The maximum MC-RR in the blood, liver and muscle of the fish was 49.7, 17.8 and 1.77 microg g(-1) DW, respectively. No MC-LR was detectable in the muscle and blood samples of the silver carp in spite of the abundant presence of this toxin in the intestines (for the liver, there was only one case when a relatively minor quantity was detected). These findings contrast with previous experimental results on rainbow trout. Perhaps silver carp has a mechanism to degrade MC-LR actively and to inhibit MC-LR transportation across the intestines. The depuration of MC-RR concentrations occurred slowly than uptakes in blood, liver and muscle, and the depuration rate was in the order of blood>liver>muscle. The grazing ability of silver carp on toxic cyanobacteria suggests an applicability of using phytoplanktivorous fish to counteract cyanotoxin contamination in eutrophic waters.

Animals↗

Controlling synthesis of silver nanowires and dendrites in mixed surfactant solutions.

Using a simple wet chemical route, high-yield silver nanowires with an average diameter of 25+/-5 nm and length up to several microm and dendrites with a long central backbone and symmetrically ramified secondary branches have been successfully obtained by reducing AgNO(3) with L-ascorbic acid (AsA) in the mixed surfactant solutions of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). It was found that the architecture of silver nanocrystals was drastically influenced by the concentrations of ascorbic acid. At a given high concentration, a nonequilibrium system was easily built, which favored the formation of fractals. When the concentration was lowered, one-dimensional silver nanowires were successfully obtained. In addition, the presence of electrolyte (NaCl) plays an important role in the preparation of silver nanowires, influencing the silver crystallization process in surprising ways.

Journal Article↗

Photochemical deposition of SERS active silver nanoparticles on silica gel and their application as catalysts for the reduction of aromatic nitro compounds.

We report an impregnation technique for immobilization of silver(I) gelatin complex on silica gel. Subsequent UV exposure of the dry impregnated silica gel deposited silver nanoparticles on the solid matrix. Conventional techniques (UV-visible spectroscopy, TEM, EDAX, and thermal analysis) have been used to identify and characterize silver particles on silica surfaces. The photoproduced silver particles have shown unique SERS activity that authenticates the presence of silver nanoclusters in the silica matrix. Hence, the surface of the silica matrix remains SERS-active for months. This surface activity of the silica matrix inspired us to successfully study the catalytic reduction of nitro-compounds in aqueous, organic, and three different micellar media. Different thermodynamic parameters for the reduction processes have also been evaluated. Catalytic activity of the particles in micelles is explained in the light of hydrophobic and electrostatic interactions between the substrate and the micelles.

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Treatment of toxic epidermal necrolysis in a pediatric patient with a nanocrystalline silver dressing.

BACKGROUND/PURPOSE: To report a case of toxic epidermal necrolysis (TEN) involving 90% body surface area, successfully treated with a nanocrystalline silver dressing (Acticoat, Smith & Nephew, Largo, FL). METHODS: A review of the hospital and acute wound center patient records and the recent English medical literature regarding TEN and nanocrystalline silver dressing. RESULTS: We found only 1 report of TEN treated with a nanocrystalline silver dressing. The nanocrystalline silver dressing was both effective in preventing wound infection and convenient for treating our patient with TEN. CONCLUSION: The use of nanocrystalline silver dressing should be considered for the treatment of TEN.

Adolescent↗

Preparation of highly concentrated stable dispersions of uniform silver nanoparticles.

Stable concentrated aqueous dispersions of silver nanoparticles of narrow size distribution were prepared by reducing silver nitrate solutions with ascorbic acid in the presence of Daxad 19 (sodium salt of a high-molecular-weight naphthalene sulfonate formaldehyde condensate) as stabilizing agent. The latter has excellent ability to prevent the aggregation of nanosize silver at high ionic strength and high concentration of metal (up to 0.3 mol dm(-3)). The presence of the dispersing agent on the surface of silver particles was confirmed by ATR-FTIR spectroscopy and electrokinetic measurements, explaining both the negative charge over the entire pH range and the electrosteric effect responsible for their long-term stability. The other experimental conditions, i.e., the pH of the reacting solutions, the concentration of the stabilizing agent, and the metal/dispersant ratio, also have a significant impact on the size and stability of these dispersions. The final nanosize silver can be obtained as dried powder, and can be fully redispersed in deionized water by sonication.

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Concentration-dependent surface-enhanced resonance Raman scattering of a porphyrin derivative adsorbed on colloidal silver particles.

Surface-enhanced Raman spectra (SERS) of 5,10,15,20-tetrakis(1-decylpyridium-4-yl)-21H,23H-porphintetrabromide or Por 10 (H(2)Tdpyp) adsorbed on silver hydrosols are compared with the FTIR and resonance Raman spectrum (RRS) in the bulk and in solution. Comparative analysis of the RR and the FTIR spectra indicate that the molecule, in its free state, has D(2h) symmetry rather than C(2v). The SERS spectra, obtained on adsorption of this molecule on borohydride-reduced silver sol, indicate the formation of silver porphyrin. With the change in the adsorbate concentration, the SERS shows that the molecule changes its orientation on the colloidal silver surface. The appearance of longer wavelength band in the electronic absorption spectra of the sol has been attributed to the coagulation of colloidal silver particles in the sol. The long wavelength band is found to be red-shifted with the decrease in adsorbate concentration. The excitation profile study indicates that the resonance of the Raman excitation radiation with the original sol band is more important than that with the new aggregation band for the SERS activity. This indicates a large contribution of electromagnetic effect to surface enhancement.

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The adsorption behavior of p-hydroxybenzoic acid on a silver-coated filter paper by surface enhanced Raman scattering.

On dried filter paper coated with silver nanoparticles, surface-enhanced Raman scattering (SERS) spectra of p-hydroxybenzoic acid (PHBA) were studied, and high-quality SERS spectra were obtained, indicating that the silver-coated filter paper is a highly SERS-active substrate. The analysis showed that the adsorption behavior of PHBA molecules on silver nanoparticles coated on filter paper was different from that in silver aqueous colloids. On the filter paper, it was found that the SERS spectra of PHBA changed with the proportion of PHBA molecules and silver nanoparticles, indicating that the adsorption behavior of PHBA molecules changed with the proportion. The probable reasons are given.

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Growth and reactivity of silver clusters in amino polycarboxylic acid solutions.

Reduction and subsequent aggregation of silver ions in the presence of various chelating agents such as trans-1,2-diaminocyclohexanetetraacetic acid (DCTA) 1,2-propylenediaminetetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetraaminehexaacetic acid (TTHA) have been studied by pulse radiolysis. Rate constants of formation and transient absorption spectra for the ligand-complexed Ag(0) and Ag(2)(+) have been determined. The redox potential of Ag(+)(L)/Ag(0)(L) becomes more negative than that of Ag(+)/Ag(0). Growth and reactivity of silver clusters were also studied in the presence of methyl viologen (MV(2+)). The kinetics of formation of the MV(+*) radical, produced by the same pulse as in the case of silver atoms, confirms the catalytic electron transfer toward super critical silver clusters in the presence of ligands. The results suggest that catalytic electron transfer activity of silver clusters depends on the ligand.

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Structure and thermal behavior of a layered silver hydroxyalkanecarboxylate.

The structure and thermal behavior of silver 16-hydroxyhexadecanoate (Ag-HHDA) have been investigated by using various analytical tools. The X-ray diffraction pattern was composed of a series of peaks that could be indexed to (0k0) reflections of a layered structure. Diffuse reflectance infrared Fourier transform spectroscopy revealed that the alkyl chains in Ag-HHDA as prepared were in an all-trans conformational state. Upon heating the sample, noticeable structural changes took place particularly in two temperature regions. The first structural change occurring at approximately 380 K was a partially irreversible one in which the binding state of carboxylate to silver converted from bridging into unidentate. A second dramatic structural change occurring at approximately 480 K was a totally irreversible process that could be associated with the decomposition of Ag-HHDA. All of these thermal characteristics of Ag-HHDA are comparable to those of silver stearate (Ag-STA). Separately, we have endeavored without success to intercalate polar molecules into the OH-group terminated layers in Ag-HHDA; the exfoliation of Ag-HHDA in various polar solvents was also unsuccessful. This is indicative of the presence of a rather stronger H-bond in Ag-HHDA, but the comparable thermal characteristics of Ag-HHDA and Ag-STA dictate that the thermal behavior of silver alkanoate is determined exclusively by the silver-to-carboxylate group interaction. This is in sharp contrast to the case of two-dimensional self-assembled monolayers for which the terminal functionalities play a crucial role in determining the structure and thermal stability of entire monolayers.

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Validation of the feeding test as an index of fear in farmed blue (Alopex lagopus) and silver foxes (Vulpes vulpes).

The reliability and validity of the eating behaviour in the presence of man (Feeding test) as an index of fear were assessed in farmed blue (Alopex lagopus) and silver foxes (Vulpes vulpes). Repeatability of the Feeding test was good in both species. No further habituation occurred after the fourth successive test in either species. In addition, the behaviour of both species was independent of the person who performed the test. The normal feeding interval, i.e., 24 h, between feed deliveries, was long enough to provide reliable results. The presence of a cage mate did not influence the blue foxes' response in the Feeding test. A significant relationship between the results of the Feeding test and the Tit-bit test in both species and between the Feeding test and fearfulness score in silver foxes indicate that all these tests measure similar features, most probably foxes' fear of humans. Those silver foxes that did not eat in the Feeding test had higher base levels of cortisol than the animals that did eat, providing further support for the above conclusion. The present study demonstrates that the Feeding test is a reliable, i.e., repeatable and free of random errors, and fairly valid fear test for blue and silver foxes. The Feeding test seems likely to give good results in measuring fear in farmed blue and silver foxes, but further investigations will be needed to fully validate it, especially for blue foxes.

Animals↗

Contribution of Spanish-American silver mines (1570-1820) to the present high mercury concentrations in the global environment: a review.

In this review I evaluate the contribution of Spanish-American silver mines during the period 1570-1820 (a Spanish colonial period of 250 years) to the present high mercury concentrations in the global environment. The evaluation is based upon the following bibliographic information: (1) total amount of mercury consumed in Spanish-American silver mines between 1570 and 1820; (2) percentage of the total amount of mercury consumed in Spanish-American silver mines that may have been emitted to the atmosphere; (3) global natural input of mercury to the atmosphere; (4) worldwide anthropogenic emissions of mercury to the atmosphere; (5) residence time of mercury in the atmosphere; and (6) capacity of mercury to be deposited in the sediments of aquatic systems. From all this information, and owing to the relatively long time that has passed since Spanish-American silver mines were operational, I conclude that most of the mercury lost during the refining of silver via the patio amalgamation process is now sequestered into the sediments of aquatic systems, mainly in marine sediments. The high mercury concentrations now being reported in the global environment essentially are a consequence of the huge pollution caused by human activities during the past 20th century.

Environmental Pollutants↗

A lipoprotein secreted by cultured hepatocytes of silver or yellow eel: comparison with their plasma lipoproteins.

Cultured hepatocytes of silver eel actively secreted only chylomicron-like lipoprotein. The rate of secretion per mg cellular protein per 24 hr was 2.2 times higher compared with that by yellow eel hepatocytes. Silver eel hepatocytes secreted lipids 2.5 times higher through the lipoprotein than yellow eel hepatocytes. Main lipid was triacylglycerol in either secreted lipoprotein and composition of apolipoproteins of both secreted lipoproteins was the same. The incorporation of 3H-leucine into the lipoprotein secreted by silver eel hepatocytes was 2.4 times higher, but that of 14C-acetate was not significantly different. Protein and lipids composition of plasma lipoproteins of silver eel was significantly higher and lower compared with those of yellow eel, respectively. We suggest that the secreted lipoprotein of silver eel hepatocytes transport much more lipids to other tissues than that of yellow eel hepatocytes.

Acetic Acid↗

11-Ketotestosterone induces silvering-related changes in immature female short-finned eels, Anguilla australis.

The developmental transition from a residential, immature 'yellow' eel to a migratory, maturing adult 'silver' eel is accompanied by many morphological changes that appear to be under endocrine control. High circulating levels of the teleost, and usually male-specific, androgen 11-ketotestosterone (11-KT) are found in migrating female short-finned eels, Anguilla australis. We examined the role of this steroid in silvering by implanting immature, female short-finned eels either with blank vehicles or with vehicles containing 11-KT. Six weeks after they had received the implants, eels treated with 11-KT had developed 'chisel-shaped' snouts and black pectoral fins with tapered ends, and the size of their eyes had increased significantly. 11-KT treated eels had a thicker dermis than control eels and an epidermis with fewer or no mucous cells. Ventricular mass at the end of the experiment was two-fold larger than in control eels. 11-KT treated eels also had larger livers and gonads. Ovaries contained predominantly cortical alveolus stage III oocytes, as opposed to the smaller gonads of control eels containing previtellogenic stage II oocytes. All of these changes correspond to changes during the developmental transition from yellow to silver eels in the wild. This demonstrates that silvering in eels is under endocrine control and that the presumed male-specific steroid 11-KT is capable of inducing silvering-related changes in a female teleost. We discuss how species-specific responses to 11-KT may differ depending on tissue-specific androgen receptor abundance and how a dual demand on liver function can explain the apparently positive effects of 11-KT on liver growth.

Animals↗

Electrochemical, spectroscopic, and mass spectrometric studies of the interaction of silver species with polyamidoamine dendrimers.

Electrochemical, spectroscopic, and mass spectrometric (MS) methods were used to probe the interaction (complexation) of silver ions and zerovalent silver species with polyamidoamine generation 1 amine-terminated (PAMAMG1NH2) and generation 2 hydroxy-terminated (PAMAMG2OH) dendrimers (DDMs). Stability constants (Kq+) and stoichiometries (q) (i.e., the number of silver ions complexed per DDM molecule) were determined from the voltammetric data, that is, shifts in potential and changes in peak or limiting current with addition of DDM. When the mole ratio of DDM to Ag+ is > or = 1, Ag+ binds with PAMAMG2OH to form a dominant 1:1 complex with a value of 1.1 x 10(7) M(-1). Under similar conditions, Ag+ binds with PAMAMG1NH2, yielding a 1:1 complex with = 4 x 10(9) M(-1), which is consistent with the finding of the MS experiments. When the mole ratio is < 1, q > or = 2. The E0' of the Ag-PAMAMG1NH2(+/0) couple shifted to a more negative value than that of the Ag(+/0) couple. The negative shift in the halfwave potential also suggests that DDM binds more strongly with Ag+ than with zerovalent silver species. Spectroscopic results suggest that hydroxyl-terminated PAMAMG2OH favors the formation of small zerovalent silver clusters after reduction while amine-terminated PAMAMG1NH2 allows for simultaneous formation of both clusters and larger nanoparticles at similar conditions. Other quantities, such as diffusion coefficients of the complexes and molar absorptivity of the Ag+ DDMs, are also reported.

Journal Article↗

Decomposition of silver carbonate; the crystal structure of two high-temperature modifications of Ag(2)CO(3).

High-resolution powder diffraction was used to study the thermal transformation of silver carbonate. A sample of Ag(2)CO(3) was heated in a capillary under 4.5 atm CO(2) pressure. The decomposition temperature of silver carbonate to silver oxide is thereby increased, allowing high-resolution synchrotron X-ray powder diffraction patterns of the two high-temperature phases of Ag(2)CO(3) to be collected. The structure of the low-temperature (lt) phase was confirmed, and the structures of the two high-temperature phases were determined by direct methods and refined using the Rietveld method: lt-Ag(2)CO(3) (295 K) P2(1)/m, z = 2, a = 4.8521(2) A, b = 9.5489(4) A, c = 3.2536(1) A, beta = 91.9713(3) degrees; beta-Ag(2)CO(3) (453 K) P31c, z = 6, a = 9.1716(4) A, c = 6.5176(3) A; alpha-Ag(2)CO(3) (476 K) P6 macro 2m, z = 3, a = 9.0924(4) A, c = 3.3249(1) A. In addition, thermal expansion properties, anisotropic microstrain distributions, and thermal transformations of the three silver carbonate phases and silver oxide are described.

Journal Article↗

Assembly of discrete, one-, two-, and three-dimensional silver(I) supramolecular complexes containing encapsulated acetylide dianion with nitrogen-donor spacers.

The first successful attempt to construct supramolecular entities via incorporation of bifunctional exodentate ligands into the silver acetylide system is reported. Coordination assembly with nitrogen-donor spacers led to the formation of five distinct supramolecular complexes, namely [(Ag(2)C(2))(AgCF(3)CO(2))(4)(pyz)(2)](n) (1), [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(CF(3)CO(2))(4)(DabcoH)(4)(H(2)O)(1.5)].H(2)O (2), [(Ag(2)C(2))(AgCF(3)CO(2))(4)(CF(3)CO(2))(bpaH)](n)() (3), [(Ag(2)C(2))(AgCF(3)CO(2))(8)(bpa)(4)](n) (4), and [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(bppz)(2)(H(2)O)](n) (5) (pyz = pyrazine; Dabco = 1,4-diazabicyclo[2.2.2]octane; bpa = 1,2-bis(4-pyridyl)ethane; bppz = 2,3-bis(2-pyridyl)pyrazine). Complex 1 is a three-dimensional framework composed of silver columns cross-linked by pyrazine bridges, whereas 2 contains a discrete supermolecule whose core is a Ag(14) double cage that is completely surrounded by trifluoroacetate, aqua, and terminal monoprotonated Dabco ligands. Complex 3 has a branched-tree architecture with one terminal of the bpa ligand attached to the silver backbone and the other exposed and protonated. In 4, neutral decanuclear [(Ag(2)C(2))(AgCF(3)CO(2))(8)] units are interlinked by bpa spacers adopting both gauche and anti conformations to generate a layer structure. Another two-dimensional network was formed with bppz serving as an angular bridging ligand in 5, in which the building unit is a silver quadruple cage containing 24 silver atoms.

Journal Article↗

Anion control of the self-assembly of 2,3-diarylpyrazines with silver(I) salts.

The synthesis and characterization of three one-dimensional coordination polymers formed on self-assembly of 2,3-diarylpyrazines with silver(I) salts are presented. A linear double-stranded coordination polymer was formed on self-assembly of 2,3-bis(3'5'-dimethylphenyl)pyrazine with silver(I) tetrafluoroborate. An essentially linear double-strand coordination polymer was formed on self-assembly of 2,3-bis(3'5'-dimethylphenyl)pyrazine with silver(I) trifluoromethanesulfonate. In contrast a helical silver-pyrazine coordination polymer with extensive intrastrand pi-stacking was formed on self-assembly of 2,3-diphenylpyrazine with silver(I) trifluoroacetate.

Journal Article↗

Tuning the coordination geometry of silver in bis(pyrazolyl)alkane complexes.

Silver(I) complexes of the bis(pyrazolyl)methane ligands Ph(2)C(pz)(2), PhCH(pz)(2), and PhCH(2)CH(pz)(2) (pz = pyrazolyl ring) have been prepared in an attempt to explore how sterically hindered poly(pyrazolyl)methane ligands influence the variable coordination geometries exhibited by silver(I) complexes, especially its ability to participate in cation...pi interactions. The complex (Ag[(pz)(2)CPh(2)](2))(PF(6)).C(3)H(6)O adopts an unusual square planar coordination environment as indicated by the sum of the four N-Ag-N angles being 360 degrees. The proximity of phenyl groups above and below the AgN(4) core enforces the unusual coordination geometry about the metal center. This arrangement is not a result of silver(I)...pi arene interactions but rather of the constraints imposed by the steric crowding caused by (aryl)(2)C(pz)(2) ligands. In contrast, the complexes of the other two ligands, (Ag[(pz)(2)CHPh](2))(PF(6)).0.5CH(2)Cl(2) and (Ag[(pz)(2)CH(CH(2)Ph)](2))(PF(6)).CH(2)Cl(2), show normal tetrahedral geometry about the silver(I), also with no indication of silver(I)...pi arene interactions. All three new complexes have extended supramolecular structures supported by a combination of CH...pi and CH...F interactions.

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