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

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

Anisotropy↗

Extending the coordination chemistry of molecular P(4)S(3): the polymeric Ag(P(4)S(3))(+) and Ag(P(4)S(3))(2)(+) cations.

Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)[Al(pftb)(4)](-) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P(4)S(3))(x)](infinity) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene.

Journal Article↗

Plastic reference electrodes and plastic potentiometric cells with dispersion cast poly(3,4-ethylenedioxythiophene) and poly(vinyl chloride) based membranes.

A simple procedure of preparing low cost, planar and disposable reference electrodes for potentiometric applications is presented. This method is essentially the same as used for obtaining all-plastic ion-selective electrodes and thus promising for simple fabrication of complete cells. Commercially available aqueous dispersion of poly(3,4-ethylenedioxythiophene) doped by poly(4-styrenesulfonate) ions (PEDOT-PSS, Baytron P) is simply cast on a non-conducting plastic support (transparent foil for laser printers). This layer is covered by a non-selective poly(vinyl chloride) based membrane containing solid AgCl and KCl, added to obtain a stable potential. The conducting polymer layer plays a double role, of electrical contact and ion-to-electron transducer, enhancing the potential stability. The reference electrodes obtained exhibit independence of the kind and concentration of electrolyte applied as well as very low sensitivity to interferences: redox reactants and H+ ions; they are also characterized by both potential stability and low polarisability, sufficient for potentiometric applications. Cells of plastic electrodes (indicator and reference ones) are tested using an arrangement with Pb2+ or Ca2+ selective sensors. Potentiometric characteristic of such cells is satisfactory, well comparable with that using a classical electrode arrangement.

Biosensing Techniques↗

Bromoderma.

A 3-year-old Japanese girl with severe epilepsy had been treated with potassium bromide since August 1999. The dose of potassium bromide was increased from 0.5 g/day to 0.8 g/day in May 2000 because of poor control of epilepsy. She also presented high fever, caused by bacterial pneumonia, in the same period. On June 11, a reddish eruption suddenly appeared on her back. Physical examination revealed grain-size, dark-red, erythematous papules and pustules on the back and face (Fig. 1). Some of the lesions on the back were ovoid to circular with small pustules and necrotic centers. Although some papules seemed to have dell in their centers, showing the appearance of herpes virus infection, Tzanck test was negative. A biopsy specimen obtained from one of the papules revealed a massive infiltration of eosinophils and neutrophils, forming an abscess in the epidermis and dermis (Fig. 2). The serum bromide level, which was 43.7 mEq/L (normal, 0-5 mEq/L) on May 25, increased to 114 mEq/L on June 14. The eruption disappeared within 10 days after the withdrawal of potassium bromide and treatment with topical sulfadiazine silver cream. The serum bromide decreased to 56.8 mEq/L on July 6.

Anti-Infective Agents, Local↗

In vitro testing of antimicrobial activity of bone cement.

The purpose of this study was to establish a reliable and cost-effective microplate proliferation assay for in vitro antimicrobial testing of bone cement samples. Cement samples devoid of antimicrobial agents, loaded with 2% gentamicin or with different concentrations of high-porosity silver, were incubated in a 96-well microplate with several staphylococcal, Pseudomonas aeruginosa, and Enterococcus faecium isolates exhibiting different susceptibilities to gentamicin. After being rinsed, the samples were brought into a soy medium in which adherent cells on the cement surface either were killed by the antimicrobial surface or started to release clonal counterparts. The medium was monitored in real time by recording a time proliferation curve for each well. Microplate testing revealed no antibacterial effect of plain bone cement. The antibacterial activity of gentamicin-loaded bone cement was shown by the microplate test to depend on the gentamicin susceptibilities of the strains. The effect of high-porosity silver was dose dependent. Bactericidal activity against all tested strains was found for bone cement loaded with 1% high-porosity silver. The accuracy of this new proliferation assay was shown by the high correlation between the types of proliferation curves and antibiotic susceptibility. In contrast to routine agar diffusion testing, it assesses the dynamic response of microorganisms to antimicrobial agents in biomaterials and allows high-throughput screening and detection of antimicrobial properties of poorly water-soluble compounds like silver.

Anti-Bacterial Agents↗

Antimicrobial properties of highly fluorinated silver(I) tris(pyrazolyl)borates.

Highly fluorinated tris(pyrazolyl)borate ligand [HB(3,5-(CF3)2Pz)3]- has been used in the isolation of air- and light-stable silver complex, [HB(3,5-(CF3)2Pz)3]Ag(OSMe2). It is a monomeric tetrahedral silver complex with an O-bonded dimethylsulfoxide ligand. The silver adduct [HB(3,5-(CF3)2Pz)3]Ag(OSMe2) and the related [HB(3,5-(CF3)2Pz)3] Ag(THF) (where OSMe2 = dimethyl sulfoxide; THF = tetrahydrofuran) show good antibacterial activity, and their antimicrobial efficacy against Staphylococcus aureus is greater than those of AgNO3 and silver sulfadiazine.

Anti-Infective Agents↗

Silver(I)-carbene complexes/ionic liquids: novel N-heterocyclic carbene delivery agents for organocatalytic transformations.

[reaction: see text] N-Heterocyclic carbene (NHC) complexes with silver were investigated as sources of unsaturated NHC carbene catalysts via thermal decomposition. The NHC complex (1-ethyl-3-methylimidazol-2-ylidene)silver(I) chloride is an ionic liquid, and was found to catalyze the ring-opening polymerization of lactide at elevated temperatures to give narrowly dispersed polylactide of predictable molecular weight. Silver-carbene complexes can also be used for the catalysis of small molecule transesterification reactions. Thermolysis of the silver complexes in the presence of CS(2) yielded the zwitterionic CS(2) adducts of the carbene, implicating the intermediacy of the free carbene in these reactions.

Catalysis↗

Determination of trace silver by solid substrate room temperature phosphorescence quenching method based on lead carboxymethyl cellulose particles (Pb(CMC)2) containing luminescent salicyl fluorenes molecules.

Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2) containing salicyl fluorones (THBF), Pb(CMC)2-THBF were synthesized by the sol-gel method, using sodium carboxymethyl cellulose (NaCMC) as precursor and Pb2+ as precipitant. Pb(CMC)2-THBF can emit the intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. And EDTA can chelate Pb2+ in Pb(CMC)2-THBF, causing it to decompose into aqueous soluble components PbY2-, CMC- and THBF, which can react with Ag+ to form Ag(CMC)2-THBF, causing the decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace silver by SS-RTP quenching method was established. The linear range of this method is 8.0-40.0 fg spot(-1) (20.0-100.0 pg ml(-1)), with a detection limit (LD) of 2.2 fg spot(-1) (corresponding to a concentration range of 5.5 x 10(-13) g ml(-1)), and the regression equation of working curve is DeltaI(p) = 12.56 + 0.5527C(Ag+) (fg spot(-1), 0.4 microl spot(-1)), n = 8, r = 0.9992. This method has been applied to the determination of trace silver in human hair and tea sample with satisfactory results. The mechanism of SS-RTP emission is also discussed.

Carboxymethylcellulose Sodium↗

Autometallography. A new technique for light and electron microscopic visualization of metals in biological tissues (gold, silver, metal sulphides and metal selenides).

The autometallographic procedure represents a new technique that can substitute for the normal methods of physical development (PD). The physical developer (a solution of reducing substance, silver salt and protection colloid) is replaced by a photographic emulsion and chemical developer. Accumulations of gold, silver, metal sulphides and metal selenides can be amplified by the present technique. Tissue sections placed on glass slides are covered by a silver bromide containing emulsion, dried and exposed to a chemical developer. After development the emulsion is either removed or cleared and the sections are counterstained and embedded. The autometallographic procedure can also be applied to ultrathin sections.

Animals↗

Crystal and solution structures of N,N-dimethylthioformamide-solvated copper(I), silver(I), and gold(I) ions studied by X-ray diffraction, X-ray absorption, and vibrational spectroscopy.

Crystal structures of the solvated copper(I) and silver(I) perchlorate salts crystallizing from N,N-dimethylthioformamide solution have been determined by single-crystal X-ray diffraction at 295 K. Tetrakis(N,N-dimethylthioformamide)copper(I) perchlorate, [Cu(SCHN(CH(3))(2))(4)]ClO(4), crystallizes in the monoclinic space group P2/n (No. 13) with a = 8.428(2), b = 9.605(2), and c = 15.096(3) A, beta = 104.35(2) degrees, and Z = 2. The copper(I) ion in a site of C(2) symmetry coordinates four N,N-dimethylthioformamide ligands in a slightly distorted tetrahedral coordination with Cu-S bond distances of 2.3249(8) and 2.3494(8) A. The triclinic (P1, No. 2) tris(N,N-dimethylthioformamide)silver(I) perchlorate, Ag(SCHN(CH(3))(2))(3)ClO(4), with a = 7.4149(5), b = 7.7953(5), and c = 17.1482(1) A, alpha = 98.341(5), beta = 93.910(5), and gamma = 107.084(5) degrees, and Z = 2, contains centrosymmetric Ag(2)(SCHN(CH(3))(2))(6)(2+) dimers in which two almost planar AgS(3) units are held together by an asymmetric double sulfur bridge with one short and one long Ag-S bond, 2.529(1) and 2.930(1) A, respectively. The Ag-S bond distances to the two terminal N,N-dimethylthioformamide ligands are 2.469(1) and 2.543(1) A. The solvated copper(I) and silver(I) ions in solution were found by means of large-angle X-ray scattering (LAXS) to coordinate four N,N-dimethylthioformamide molecules with the mean Cu-S and Ag-S bond distances 2.36(1) and 2.58(1) A, respectively, probably with distorted tetrahedral coordination geometry, while an EXAFS study gave the Cu-S bond distance 2.34(1) A. EXAFS studies showed a linear S-Au-S entity with an Au-S bond distance of 2.290(5) A in the structure of the solid bis(N,N-dimethylthioformamide)gold(I) tetrafluoroborate, Au(SCHN(CH(3))(2))(2)BF(4). The structure in solution is similar with a mean Au-S bond distance of 2.283(4) A. Raman and infrared vibrational spectra of the solvated copper(I), silver(I), and gold(I) ions in the solid state and N,N-dimethylthioformamide solution have been recorded and assigned.

Absorptiometry, Photon↗

Topical treatment of the burn patient.

The pathophysiology, classification and bacteriology of burns are discussed, as well as treatment of burns with silver nitrate, silver sulfadizine, silver allantoinate, mafenide acetate, furazolium chloride, povidone-iodine complex, antibiotics, antiproteolytics, fibrinolytics, Pseudomonas vaccine and antiglobulins.

Administration, Topical↗

Measurement of ultrasmall volumes using anodic stripping voltammetry.

This paper discusses a new and effective method for small volume determination. The benefits of working with small volumes are numerous and include using less material, generating less waste, increased functionality in less space, portability, and high throughput. As sample size decreases, measuring its volume becomes more challenging. The most prevalent method for small volume determination is visual inspection. The method presented in this paper is precise, more quantitative, and adaptive to many solution geometries, because it is based on a coulometric approach. Demonstration of this method is performed on volumes of approximately 1 nL containing silver and using a self-contained microcavity device that contains multiple electrodes. The silver is "exhaustively" deposited during a cathodic potential step, followed by anodic stripping voltammetry. It is expected that an even faster and more accurate analysis of volumes much smaller than those evaluated here is easily possible using this approach.

Chemistry Techniques, Analytical↗

[Complexing mechanism on extraction of DHA ester using silver ion].

Ultraviolet spectra of docosahexaenoic acid (DHA) ester and its complex with silver ion were determined, and shifts of ultraviolet absorption peak before and after the complexing reaction were observed. Meanwhile, complexing bonds of DHA ester-silver ion were explained by molecular orbital theory. Thus, complex structure and complexing mechanism were discovered. The results showed that ultraviolet characteristic absorption peak of DHA ester-silver ion complex moved to lower wavelength. It pointed out that distance between energy levels for outer electron transition of complex is increased, and the energy for outer electron transition of complex is bigger than that of DHA ester.

Chelating Agents↗

[Cytocompatibility of dental alloys containing palladium].

The cytoxicity and the 50% lethal concentration (LC50) has been assessed in vitro by the colony forming method in extracts of 5 precious or semiprecious alloys and of oxides and chlorides of the metal contained in these alloys: Pd, Ag, Cu, Zn, Sn, In and Ga. All alloy extracts in culture medium induced cell death depending on their composition. In, Ga and Sn compounds showed the most favorable cell viability, Cu and Ag salts induced the lowest survival rate.

Biocompatible Materials↗

A family of ductile intermetallic compounds.

Stoichiometric intermetallic compounds have always been touted for their attractive chemical, physical, electrical, magnetic and mechanical properties, but few practical uses have materialized because they are brittle at room temperature. Here we report on a large family of fully ordered, stoichiometric binary rare-earth intermetallic compounds with high ductility at room temperature. Although conventional wisdom calls for special conditions, such as non-stoichiometry, metastable disorder or doping to achieve some ductility in intermetallic compounds at room temperature, none of these is required in these unique B2 rare-earth compounds. Ab initio calculations of YAg, YCu and NiAl crystal defect energies support the observed deformation modes of these intermetallics.

Anisotropy↗