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At least 19 records

All that is silver is not toxic: silver ion and particle kinetics reveals the role of silver ion aging and dosimetry on the toxicity of silver nanoparticles

When suspended in cell culture medium, nano-objects composed of soluble metals such as silver can dissolve resulting in ion formation, altered particle properties (e.g. mass, morphology, etc.), and modulated cellular dose. Cultured cells are exposed not just to nanoparticles but to a complex, dynamic mixture of altered nanoparticles, free ions, and ion-ligand complexes. Here, three different cell types (RAW 264.7 macrophages and bone marrow derived macrophages from wild-type C57BL/6J mice and Scavenger Receptor A deficient (SR-A (-/-) ) mice) were exposed to 20 and 110 nm silver nanoparticles, and RAW 264.7 cells were exposed to freshly mixed silver ions, aged silver ions (ions incubated in cell culture medium), and ions formed from nanoparticle dissolution. The In Vitro Sedimentation, Diffusion, Dissolution, and Dosimetry Model (ISD3) was used to predict dose metrics for each exposure scenario. Silver nanoparticles, freshly mixed ions, and ions from nanoparticle dissolution were toxic, while aged ions were not toxic. Macrophages from SR-A (-/-) mice did not take up 20 nm silver nanoparticles as well as wild-types but demonstrated no differences in silver levels after exposure to 110 nm nanoparticles. Dose response modeling with ISD3 predicted dose metrics suggest that amount of ions in cells and area under the curve (AUC) of ion amount in cells are the most predictive of cell viability after nanoparticle and combined nanoparticle/dissolution-formed-ions exposures, respectively. Results of this study suggest that the unbound silver cation is the ultimate toxicant, and ions formed extracellularly drive toxicity after exposure to nanoparticles. Applying computational modeling (ISD3) to better understand dose metrics for soluble nanoparticles allows for better interpretation of in vitro hazard assessments.

60 APPLIED LIFE SCIENCES↗

Deformation Twinning of a Silver Nanocrystal under High Pressure

Within a high-pressure environment, crystal deformation is controlled by complex processes such as dislocation motion, twinning, and phase transitions, which change materials' microscopic morphology and alter their properties. Understanding a crystal's response to external stress provides a unique opportunity for rational tailoring of its functionalities. It is very challenging to track the strain evolution and physical deformation from a single nanoscale crystal under high-pressure stress. Here, we report an in situ three-dimensional mapping of morphology and strain evolutions in a single-crystal silver nanocube within a high-pressure environment using the Bragg Coherent Diffractive Imaging (CDI) method. We observed a continuous lattice distortion, followed by a deformation twining process at a constant pressure. The ability to visualize stress-introduced deformation of nanocrystals with high spatial resolution and prominent strain sensitivity provides an important route for interpreting and engineering novel properties of nanomaterials.

coherent diffractive imaging↗

Electric field enhancement in a self-assembled 2D array of silver nanospheres

We investigate the plasmonic properties of a self-assembled 2D array of Ag nanospheres (average particle diameter/inter-particle separation distance of 9/3.7 nm). The structures of the individual particles and their assemblies are characterized using high-resolution transmission electron microscopy (HR-TEM). The plasmonic response of the nanoparticle network is probed using two-photon photoemission electron microscopy (TP-PEEM). HR-TEM and TP-PEEM statistics reveal the structure and plasmonic response of the network to be homogeneous on average. This translates into a relatively uniform surface-enhanced Raman scattering (SERS) response from biphenyl,4-4{sup ′}-dithiol (BPDT) molecules adsorbed onto different sites of the network. Reproducible, bright, and low-background SERS spectra are recorded and assigned on the basis of density functional theory calculations in which BPDT is chemisorbed onto the vertex of a finite tetrahedral Ag cluster consisting of 20 Ag atoms. A notable agreement between experiment and theory allows us to rigorously account for the observable vibrational states of BPDT in the ∼200–2200 cm{sup −1} region of the spectrum. Finite difference time domain simulations further reveal that physical enhancement factors on the order of 10{sup 6} are attainable at the nanogaps formed between the silver nanospheres in the 2D array. Combined with modest chemical enhancement factors, this study paves the way for reproducible single molecule signals from an easily self-assembled SERS substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical properties of silver, silver sulfide and silver selenide nanoparticles and antibacterial applications

Highlights: • Ag small nanoparticles synthesis in zeolite A4. • SERS effect in Ag small nanoparticles. • Bactericidal properties in Ag{sub 2}Se and Ag{sub 2}S semiconductor nanoparticles. - Abstract: This work presents the optical properties and antibacterial activity of silver nanoparticles (AgNPs) and their semiconductors from S and Se (Ag{sub 2}S and Ag{sub 2}Se nanoparticles). The nanoparticles were synthesized and stabilized in the matrix of the synthetic zeolite A4. Both compounds Ag{sub 2}S and Ag{sub 2}Se nanoparticles show a size of around 9 nm and quasi-spherical morphology. The interplanar distances calculated in the TEM images confirm the presence of metallic and semiconductor nanoparticles with hexagonal, monoclinic and orthorhombic structures for nanoparticles Ag, Ag{sub 2}S and Ag{sub 2}Se, respectively. The Surface plasmon resonance for AgNPs was obtained around 415 nm. Furthermore, in nanoparticles Ag{sub 2}S and Ag{sub 2}Se we identified absorptions bands in the visible region with maxima around 330 and 375 nm. The presence of SERS effect caused by metallic nanoparticles on the surface of the zeolite was observed. The antibacterial activity of the nanoparticles stabilized in the zeolite was analyzed against gram-negative bacteria and gram-positive bacteria.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques

Here, the structure of pristine AgFeO 2 and phase makeup of Ag 0.2 FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2 O 3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2 FeO 1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe 2 O 3 component in the Ag 0.2 FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2 FeO 1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+y Fe III Fe II yO 2 phase. The Li 1+y Fe III Fe II yO 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2 FeO 1.6 composite, a substantial amorphous γ-Fe 2 O 3 component is observed which discharges to rock salt LiFe 2 O 3 and Fe 0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.

25 ENERGY STORAGE↗

Geometrical parameters effects on local electric field enhancement of silver-dielectric-silver multilayer nanoshell

The local electric field enhancement at different points of silver-dielectric-silver nanoshell is investigated using quasi-static theory. Because of the symmetric and anti-symmetric coupling between surface plasmon of inner silver core and outer silver shell, the local electric field spectrum of silver-dielectric-silver has two distinct peaks at resonance wavelengths. The silver core size and middle dielectric thickness affect the local electric field enhancement at different points of silver-dielectric-silver nanoshell. Increasing the silver core radius always leads to blue shift of shorter resonance wavelength and red shift of longer resonance wavelength. We observed two distinct local electric field peaks, which are corresponded to the symmetric and anti-symmetric coupling between inner and outer surface plasmons. In a system with thick silver shell, local electric field enhancement is greater than a system with thin silver shell. However, the local electric field variations as a function of silver core radius in both systems are different at different points of nanoshell. The effects of the dielectric thickness variations on local electric field are different from those from silver core size variations. As the dielectric thickness is about 3 nm, the highest local electric field enhancement occurs at the surface of the inner silver core, where the symmetric and anti-symmetric modes are mixed together.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optimization of silver-dielectric-silver nanoshell for sensing applications

In this paper, resonance light scattering (RLS) properties of a silver-dielectric-silver nanoshell, based on quasi-static approach and plasmon hybridization theory, are investigated. Scattering spectrum of silver-dielectric-silver nanoshell has two intense and clearly separated RLS peaks and provides a potential for biosensing based on surface plasmon resonance and surface-enhanced Raman scattering. The two RLS peaks in silver-dielectric-silver nanoshell are optimized by tuning the geometrical dimensions. In addition, the optimal geometry is discussed to obtain the high sensitivity of silver-dielectric-silver nanoshell. As the silver core radius increases, the sensitivity of silver-dielectric-silver nanoshell decreases whereas increasing the middle dielectric thickness increases the sensitivity of silver-dielectric-silver nanoshell.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Selective recovery of silver from waste low-temperature co-fired ceramic and valorization through silver nanoparticle synthesis

Highlights: • Silver rich LTCC an e-waste has been recycled and valorized. • Selectively, Ag was leached and recovered as nanopowder. • The process can circulate the Ag within the industry in a close loop. • Brings back the material to production stream and address the circular economy. • Can be part of cradle-to-cradle technology and lower the futuristic carbon economy. - Abstract: Considering the value of silver metal and silver nanoparticles, the waste generated during manufacturing of low temperature co-fired ceramic (LTCC) were recycled through the simple yet cost effective process by chemical-metallurgy. Followed by leaching optimization, silver was selectively recovered through precipitation. The precipitated silver chloride was valorized though silver nanoparticle synthesis by a simple one-pot greener synthesis route. Through leaching-precipitation optimization, quantitative selective recovery of silver chloride was achieved, followed by homogeneous pure silver nanoparticle about 100 nm size were synthesized. The reported recycling process is a simple process, versatile, easy to implement, requires minimum facilities and no specialty chemicals, through which semiconductor manufacturing industry can treat the waste generated during manufacturing of LTCC and reutilize the valorized silver nanoparticles in manufacturing in a close loop process. Our reported process can address issues like; (i) waste disposal, as well as value-added silver recovery, (ii) brings back the material to production stream and address the circular economy, and (iii) can be part of lower the futuristic carbon economy and cradle-to-cradle technology management, simultaneously.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigation of Reactive Silver Ink Formula for Reduced Silver Consumption in Silicon Heterojunction Metallization

Silver is the most expensive non-silicon component in photovoltaic cells. This is particularly salient for silicon heterojunction (SHJ) cells, which rely on large quantities of low-temperature silver pastes (LT-SP). SHJ cells would benefit greatly from an industrially scalable metallization process that simultaneously offers low silver consumption, low finger resistivities (<20 μΩ·cm), and low processing temperatures. Printed reactive silver inks (RSI) are an innovative candidate to this end. Furthermore, this work furthers the research on RSI metallization by investigating the impact of ink formula on properties pertinent to SHJ cells, including electrical properties, line width, ink splatter, silver consumption, cell performance, and adhesion. We introduce a scalable, high-throughput flexible needle contact printing approach for metallization that solves many of the issues associated with drop-on-demand printing. The printed silver fingers are characterized using electrical measurements and top-down and cross-sectional microscopy. The best performing ink, consisting of silver acetate, ethylamine, and formic acid, achieved silver fingers with total resistivities of 3.1 μΩ·cm and contact resistivities of 3.2 mΩ·cm 2 when printed at 61 °C. This ink metallized a full-sized 156 mm × 156 mm SHJ cell. This is the first reported data for RSI metallization of a full-sized SHJ cell and shows how an optimized RSI can achieve similar performances to LT-SP while consuming 80–90% less silver.

14 SOLAR ENERGY↗

Corrosion of novel reactive silver ink and commercial silver-based metallizations in diluted acetic acid

Silver-based metallizations in photovoltaic modules are susceptible to corrosion by acetic acid generated in ethylene vinyl acetate encapsulated modules, resulting in power losses over time. Here, three silver-based metallizations are exposed to diluted acetic acid, in concentrations representative of that found in field-exposed modules. Compositional, morphological, and structural changes of the metallizations are studied over 3000 h of exposure to diluted acetic acid using Raman spectroscopy mapping, X-ray diffraction, and scanning electron microscopy. The three metallizations studied are: 1) a commercial high-temperature fire-through Ag paste, commonly used for Si diffused junction solar cells; 2) a commercial low-temperature paste normally used for silicon heterojunction cells; and 3) a novel low-temperature reactive silver ink shown to be suitable for photovoltaic applications. We find distinct corrosion rates for the high-temperature silver paste and reactive silver ink in the presence of diluted acetic acid. However, the low-temperature silver paste appears to be more corrosion resistant, likely due to a polymer layer that protects the silver particles.

36 MATERIALS SCIENCE↗

Speciation Matters: Bioavailability of Silver and Silver Sulfide Nanoparticles to Alfalfa ( Medicago sativa )

Terrestrial crops are directly exposed to silver nanoparticles (Ag-NPs) and their environmentally transformed analog silver sulfide nanoparticles (Ag 2 S-NPs) when wastewater treatment biosolids are applied as fertilizer to agricultural soils. This leads to a need to understand their bioavailability to plants. In the present study, the mechanisms of uptake and distribution of silver in alfalfa (Medicago sativa) were quantified and visualized upon hydroponic exposure to Ag-NPs, Ag 2 S-NPs, and AgNO 3 at 3 mg total Ag/L. Total silver uptake was measured in dried roots and shoots, and the spatial distribution of elements was investigated using transmission electron microscopy (TEM) and synchrotron-based X-ray imaging techniques. Despite large differences in release of Ag + ions from the particles, Ag-NPs, Ag 2 S-NPs, and Ag + became associated with plant roots to a similar degree, and exhibited similarly limited (<1%) amounts of translocation of silver into the shoot system. X-ray fluorescence (XRF) mapping revealed differences in the distribution of Ag into roots for each treatment. Silver nanoparticles mainly accumulated in the (columella) border cells and elongation zone, whereas Ag + accumulated more uniformly throughout the root. In contrast, Ag 2 S-NPs remained largely adhered to the root exterior, and the presence of cytoplasmic nano-Si x O y aggregates was observed. Exclusively in roots exposed to particulate silver, NPs smaller than the originally dosed NPs were identified by TEM in the cell walls. Lastly, the apparent accumulation of Ag in the root apoplast determined by XRF, and the presence of small NPs in root cell walls suggests uptake of partially dissolved NPs and translocation along the apoplast.

54 ENVIRONMENTAL SCIENCES↗

Effect of silver doping on the surface of La{sub 5/8}Ca{sub 3/8}MnO{sub 3} epitaxial films

Thin film manganese oxides (manganites) display remarkable properties, such as colossal magnetoresistance and charge ordered phases, and became a focal point of research in the past two decades owing to potential applications ranging from oxide spintronics to resistive switching-based memories. La{sub x}Ca{sub 1−x}MnO{sub 3} (LCMO), a widely studied manganite, is known to substantially improve its transport properties when doped with Ag. However, despite the abundance of studies on LCMO, the effect of silver on the surface structure is unknown. Here, through in-situ methods, scanning tunneling microscopy (STM) is performed on La{sub 5/8}Ca{sub 3/8}MnO{sub 3} films grown by pulsed laser deposition. Films doped by silver, as confirmed by in-situ X-ray photoelectron spectroscopy, display large-scale reconstructions, interpreted as being of type (√10 × √10)R18.4°, while films lacking silver display a (√2 × √2)R45° reconstruction that may be associated with a surface charge-ordered state. It is posited that the possible cause of the varied reconstructions is due to a vacancy ordering on top of the existing (√2 × √2)R45° reconstruction. These studies highlight the influence of Ag on the surface structure, and therefore a route towards modifying the surface properties of manganites.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗