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The silver-silver chloride electrode: a possible generator of offset voltages and currents.

Large input currents can be generated by an asymmetry in the chloride activity seen by Ag-AgCl electrodes used at the input of intracellular amplifiers because offset compensation no longer takes place at the input of the amplifier but rather later in the circuit in many modern amplifiers. This situation occurs when chloride-free solution, such as potassium acetate, potassium citrate or various intracellular dyes are used as pipette and electrode holder filling solutions. Omitting the agar bridge at the reference electrode, or using a platinum electrode will have similar results. Values of cellular membrane potentials can be significantly contaminated under such conditions, particularly where the amplifier input resistance did not exceed 10(10) omega and where small cells were studied. Unexpected iontophoresis of Cl- can occur when the asymmetry is such as to make the recording pipette negative. These offsets can be avoided in all situations by the use of salt bridges which insure that the two Ag/AgCl junctions are in contact with Cl- of the same activity.

Electrophysiology↗

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↗

Internal redistribution of radiolabelled silver among tissues of rainbow trout (Oncorhynchus mykiss) and European eel (Anguilla anguilla): the influence of silver speciation.

Influence of water Ag(I) speciation on pharmacokinetics of Ag(I) during a post-exposure period was investigated in rainbow trout (Oncorhynchus mykiss) and European eel (Anguilla anguilla). The rainbow trout is sensitive to waterborne ionic Ag(+) whereas the eel is tolerant. The fish were acclimated to either of two chloride concentrations, 10 or 1200 microM, in synthetic soft water and then exposed to a sublethal 24-h pulse of 1.3 microgl(-1) of 110mAg(I) added as 110mAgNO(3) in these waters. The protocol provided exposures to mainly the free ion Ag(+) (low chloride water) or mainly AgCl(aq) (high chloride water). Contents and concentrations of 110mAg(I) in tissues and body fluids were then monitored over a 67-day post-exposure period in Ag(I)-free water of the same chloride levels. Changing the speciation of Ag(I) in the water had no effect on the whole body load of 110mAg(I), but did result in differences in internal distribution. In trout, changing water Ag(I) speciation significantly altered elimination or accumulation of Ag(I) in several body compartments. Notably, trout exposed to AgCl(aq) eliminated 110mAg(I) from the kidney more quickly than trout exposed to Ag(I) primarily as Ag(+). This elimination was matched by higher concentrations of 110mAg in liver of trout exposed to Ag(I) primarily as AgCl(aq). In eel, shifting speciation from Ag(+) to AgCl(aq) hastened elimination of 110mAg(I) from mid and posterior intestine and increased 110mAg(I) retention in kidney. While there was no difference between the two fish species in whole body 110mAg(I) load, most internal body compartments of trout had higher 110mAg(I) concentrations than those in eel early in the experiment. Because tissue-specific elimination times were longer in eel than in trout, these differences were generally cancelled by the end of the 67-day depuration period. The only exception was the liver, which in trout continued to accumulate 110mAg(I) throughout the experiment but in eel remained unchanged. The combined effect of 110mAg(I) movements in the two species was that trout retained all their accumulated 110mAg(I) through the 67-day period, whereas the body burden of 110mAg(I) in eel was reduced to half initial values by day 67.

Adaptation, Physiological↗

Ultrasound-facilitated transport of silver chloride (AgCl) particles in fish skin.

Electron-dense nano-particles in aqueous suspension were administered by immersion into the epidermis of fish using ultrasound in the therapeutic range. Enhanced permeability of the tissues to the particles was achieved by acoustic cavitation, which induced a controlled level of necrosis in the outer cell layers, and by non-cavitational exposures, which widened intercellular spaces of non-necrosed tissue in deeper regions of the epidermis. Both particle concentration and penetration depth were quantified using transmission electron microscopy. While cavitation-induced perforation was necessary for particles to penetrate into the tissues, non-cavitational exposures during immersions increased the particle flux towards the skin surface, as well as the diffusion rate of the particles within the epidermis and their depth of penetration. The technique described above may potentially be applied for non-stressful, mass-administration of substances into aquatic animals, as well as the relatively new field of ultrasound-facilitated delivery in moist epithelial tissues in humans.

Animals↗

Ground-based studies with Super-Dwarf wheat in preparation for space flight.

Several experiments were carried out to test responses of a Super-Dwarf cultivar of wheat (Triticum aestivum L.) to various environmental parameters that were anticipated to be present in our attempts to grow the wheat in a small growth chamber on the Russian Space Station, Mir, or that proved to be present in a 1995 trial space experiment. Under low photosynthetic photon flux (40-400 micromoles m-2 s-1 PPF), development (e.g. anthesis) was retarded, but heads (often sterile) always formed, even if light was so low that plants died before the heads could mature. Longer photoperiods promoted flowering, but night interruptions combined with short days did not provoke a long-day response as occurs with true long-day plants. The long-day effect could prove to be a summation of photosynthetic products. Heat stress (40 degrees C for 1-24 h) did not influence flowering but killed plants that were 13-16-day-old (no effect on younger plants). Concentrations of iodine or silver-fluoride disinfectants present in the water used for plants on Mir (1.0-4.0 mg L-1) did not affect plant growth although higher concentrations (8.0-1.6 mg L-1) were inhibitory. GA3 or indoleacetic acid applied every other day at concentrations from 1.0 x 10(-6) mg L-1 to 3.162 x 10(-4) mg L-1 did not change the height of Super-Dwarf wheat, suggesting that this cultivar is not a gibberellin mutant.

Disinfectants↗

Innovative technology for tissue disruption by explosive-induced shock waves.

We have developed a novel, less invasive, shock wave source that can be introduced into an arbitrary position in a human body percutaneously. Using this technique we can disrupt cells locally. The shock wave source consists of an explosive, an optical fiber, a balloon catheter, and a Nd:YAG laser, which generates a spherical explosive shock wave. The destructive potential of the present source for injuring tissue was confirmed and the subsequent cell elongation and split in the direction of the shock wave has been observed.

Animals↗

Separation and detection of closely related endorphins by liquid chromatography-electrochemistry.

The specific aim of this study was to investigate the selectivity of liquid chromatography--electrochemistry for minor variations in the structure of small endorphins. Using isocratic mobile phases, chromatographic conditions were established for the separation of a series of closely related endorphins. Hydrodynamic voltammetry showed that each peptide exhibited a characteristic oxidative behavior that was also reflected in peak current ratios. Changes in a small moiety altered both the chromatographic behavior and electroactivity of these neuropeptides.

Chromatography, Liquid↗

Antimicrobial properties of silver-containing wound dressings: a microcalorimetric study.

The studies reported here have been undertaken to assess the potential use of isothermal microcalorimetry in studying the antimicrobial efficacy of wound dressings that contain antimicrobial agents. The microcalorimetric technique allows non-invasive and non-destructive analysis to be performed directly on a test sample, regardless of whether it is homogeneous or heterogeneous in nature. Microcalorimetry is an established procedure that offers quantitative measurements and has the distinct advantage over traditional antimicrobial test methodologies in that calorimetric measurements are made continuously over real-time, thus the dynamic response of microorganisms to an antimicrobial agent is observed in situ. The results described in this paper are for interaction of two silver-containing wound care products AQUACEL Ag Hydrofiber (ConvaTec, Deeside, UK) and Acticoat 7 with SILCRYST (Smith and Nephew Healthcare, UK) with the wound pathogenic organisms Staphylococcus aureus and Pseudomonas aeruginosa. Both dressings are shown, microcalorimetrically, to have the capacity to kill these common wound pathogens within 1-2 h of contact. A dose-response study was conducted with the AQUACEL Ag dressing. Microcalorimetry is shown to be rapid, simple and effective in the study of the antimicrobial properties of gel forming wound dressings.

Anti-Infective Agents↗

Catheter-associated urinary tract infections: impact of catheter materials on their management.

Infection associated with an indwelling catheter is a representative type of biofilm infection occurring in the urinary tract. Since the most effective way to control this intractable infection is the prevention of bacterial attachment and subsequent biofilm formation on the catheter, the importance of catheter materials and anti-bacterial coating cannot be underestimated. The difference in the degree of bacterial attachment among standard catheter materials, the efficacy of silver-coating of catheters in preventing infection and the potency and effectiveness of a new lecithin/silver coating are discussed.

Anti-Infective Agents, Urinary↗

Ag/AgCl/Cl- coated silver-stripe reference electrode.

This paper introduces a new type of miniaturized coated silver-stripe reference electrode without internal solution for single use and intends to give in detail the method used to prepare a Ag/AgCl/Cl- miniaturized coated silver-stripe reference electrode of a second kind which acts as a half-cell of a sensor system measuring Ca2+ ion activity in human blood as well as the difficulties encountered. The technique described is a cost-effective and time saving method for biomedical measurement.

Biomedical Engineering↗

Surface-enhanced raman scattering of p-nitrothiophenol molecular vibrations of its silver salt and the surface complex formed on silver islands and colloids.

The interpretation of the surface-enhanced Raman scattering (SERS) spectra of p-nitrothiophenol (p-NTP) is reported. SERS spectra were obtained by vacuum evaporation and casting of p-NTP onto silver island films, and also from colloidal silver solutions. The vibrational spectra of the silver salt (p-NTP-silver) were obtained for a direct comparison with the SERS of p-NTP chemically adsorbed onto Ag. Chemisorption of p-NTP through S-Ag bonding is indirectly proven by the disappearance of the S-H stretching mode. The Raman scattering spectrum of the silver salt is in good agreement with the SERS spectra of the silver surface complex. The spectral interpretation was aided using density functional theory calculations of the molecular spectra of p-NTP and that of the Ag-p-NTP.

Colloids↗

Surface enhanced Raman spectroscopic studies of 1H-indazole on silver sols.

The SER spectra of 1H-indazole adsorbed on silver hydrosol were recorded in the 1800-100 cm(-1) and in the 3200-2800 cm(-1) regions. The SERS data were interpreted on the basis of previous vibrational assignments, with the help of the results of DFT calculations carried out using the 6-31G** basis. From the comparison of SER and normal Raman spectra it can be deduced that 1H-indazole is non-dissociatively adsorbed on metal surface and that it interacts with silver sol via nitrogen atoms and ring pi-system. The molecular plane assumes a tilted orientation with respect to the silver surface. The effect of varying the concentration of adsorbate was also evaluated. The observed changes of the relative intensities of some enhanced bands suggest that the molecule assumes a more tilted orientation upon lowering the concentration of the adsorbate.

Indazoles↗

Vibrational spectra of 1-methyluracilate complex with silver(I) and theoretical studies of the 1-MeU anion.

The FT-Raman and FT-infrared spectra of (1-methyluracilato)silver, [Ag(C(5)H(5)N(2)O(2))] in the solid state have been studied. The complex is a polymer in which one silver ion is linearly bonded to two 1-MeU ligands through the deprotonated N(3) sites and another silver ion is tetrahedrally coordinated to the four 1-MeU ligands through the O2 and O4 carbonyl oxygen atoms. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of the N(3)-deprotonated 1-methyluracilate anion have been calculated using density functional (B3LYP) and ab initio (HF and MP2) methods with the 6-31G(d,p) and 6-31++G(df,pd) basis sets. The calculated potential energy distribution (PED) for the 1-MeU anion has proved to be of great help in assigning the spectra of the title complex. It can be concluded that the two strong Raman bands at 1263 and 796 cm(-1) are diagnostic for the N3-deprotonation of the 1-methyluracilate ring and complexation with silver ion. The linear N-Ag-N stretching vibrations are assigned to the bands at 448 and 362 cm(-1) (IR) and 453, 362 cm(-1) (Raman). The Ag-O stretching vibrations are assigned to the bands in the range of 280-250 cm(-1).

Anions↗

Semi-quantitative analysis of indigo carmine, using silver colloids, by surface enhanced resonance Raman spectroscopy (SERRS).

The application of surface enhanced resonance Raman spectroscopy (SERRS) to the semi-quantitative analysis of the dye, indigo carmine, has been examined using citrate-reduced silver colloids. Good linear correlations are observed for the dye band at 1580 cm(-1) in the concentration range 10(-7)-10(-5) and 10(-9)-10(-5) mol dm(-3), using laser exciting wavelengths of 514.5 [(R=0.9983)] and 632.8 nm [(R=0.9978)], respectively. At concentrations of dye above 10(-6) M the concentration dependence of the SERRS signals is non-linear due to the coverage of the surface of the colloidal particles by the dye being in excess of a full monolayer. At concentrations above 10(-6) M resonance Raman spectroscopy (RRS) can be employed for the quantitative analysis of the dye. An internal standard was used and a good linear correlation (R=0.997) was observed for the dependence of dye signal intensities at 1580 cm(-1) in the concentration range 10(-5)-10(-4) M using a laser exciting wavelength of 514.5 nm. The limits of detection of indigo carmine by SERRS (514.5 nm), SERRS (632.8 nm) and solution RRS (514.5 nm) are found to be 0.9, 1 and 38 ppm, respectively.

Colloids↗

Semi-quantitative analysis of indigo by surface enhanced resonance Raman spectroscopy (SERRS) using silver colloids.

In this paper we report for the first time semi-quantitative analysis of indigo using surface enhanced Raman spectroscopy (SERS) and surface enhance resonance Raman spectroscopy (SERRS). Indigo, a dye widely used today in the textile industry, has been used, historically, both as a dye and as a pigment; the latter in both paintings and in printed material. The molecule is uncharged and largely insoluble in most solvents. The application of SERS/SERRS to the semi-quantitative analysis of indigo has been examined using aggregated citrate-reduced silver colloids with appropriate modifications to experimental protocols to both obtain and maximise SERRS signal intensities. Good linear correlations are observed for the dependence of the intensities of the SERRS band at 1151 cm(-1) using laser exciting wavelengths of 514.5 nm (R=0.9985) and 632.8 nm (R=0.9963) on the indigo concentration over the range 10(-7)-10(-5) and 10(-8)-10(-5) mol dm(-3), respectively. Band intensities were normalised against an internal standard (silver sol band at 243 cm(-1)). Resonance Raman spectra (RRS) of aqueous solutions of indigo could not be collected because of its low solubility and the presence of strong fluorescence. It was, however, possible to obtain RS and RRS spectra of the solid at each laser excitation wavelength. The limits of detection (L.O.D.) of indigo by SERS and SERRS using 514.5 and 632.8 nm were 9 ppm at both exciting wavelengths. Signal enhancement by SERS and SERRS was highly pH dependent due to the formation of singly protonated and possibly doubly protonated forms of the molecule at acidic pH. The SERS and SERRS data provide evidence to suggest that an excess of monolayer coverage of the dye at the surface of silver colloids is observed at concentrations greater than 7.85x10(-6) mol dm(-3) for each exciting wavelength. The data reported herein also strongly suggest the presence of multiple species of the indigo molecule.

Colloids↗

Characterization and surface-enhanced Raman spectral probing of silver hydrosols prepared by two-wavelength laser ablation and fragmentation.

A four step Ag foil laser ablation-Ag nanoparticle fragmentation procedure in ultrapure water was carried out both under argon and in air. Pulses of a high power Nd/YAG laser were used for laser ablation (1064 nm) and for the three step Ag hydrosol treatment in the absence of Ag foil in the sequence 1064-532-1064 nm. Transmission electron microscopy (TEM) and surface plasmon (SP) extinction spectra provide evidence of Ag nanoparticle fragmentation in the second and third step of the procedure carried out under argon. While polydispersity of Ag hydrosol increases in the second step, both the polydispersity and the mean size of the nanoparticles are reduced in the third step. Qualitative and quantitative surface-enhanced Raman scattering (SERS)/surface-enhanced resonance Raman scattering (SERRS) spectral probing of systems with Ag hydrosols and the selected adsorbates at 514.5 nm excitation shows that Ag hydrosols obtained in the second step of the preparation procedure carried out in air are the most suitable substrates for SERS/SERRS experiments performed at this excitation wavelength.

Silver Compounds↗

Magnetic resonance study of Rh complexes in AgCl microcrystals.

X-ray or UV irradiation at room temperature of Rh3+ doped AgCl emulsion powders leads to the production of three paramagnetic Rh2+ related centres, labeled R4, R5 and R6. A combined X and Q band electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) study allowed the determination of a nearly complete structural model for these centres. In the X band ENDOR spectra of R4 and R5 interactions of the unpaired electron with nearby protons have been identified, indicating that for these centres Cl- ligands have been exchanged by H2O or OH-. The R6 centre, identified as a (RhCl6)4- complex, has been found to be fundamentally different from the dominant centre in large Rh2+ doped AgCl single crystals grown from the melt. The results are compared with recent work by other researchers in the same field.

Crystallization↗

Sequential-injection stripping analysis of nifuroxime using DNA-modified glassy carbon electrodes.

The voltammetric behavior of nifuroxime was investigated comparing stationary voltammetric methods with the recently proposed sequential-injection stripping analysis (SISA), by using cyclic voltammetry (CV) and differential-pulse voltammetry at bare and DNA-modified glassy carbon (GC) electrodes. In cyclic voltammetry, reduction of nifuroxime at DNA-modified electrodes gives rise to a well-defined peak, and in contrast to bare GC surfaces, a re-oxidation peak could be observed. Optimization of the pre-concentration process at the DNA-modified surface led to a significant enhancement of the voltammetric current response, a better defined peak shape and an improved dynamic range. Based on this optimized voltammetric procedure, SISA has been evaluated for the determination of nifuroxime. The flow-system significantly facilitates the regeneration of the DNA-modified electrode surface, hence diminishing problems related to accumulation and memory effects. The linear detection range could be extended to 65 microM with a detection limit (3 s) of 0.68 microM, which corresponds to an absolute amount of 21 ng nifuroxime.

Biosensing Techniques↗