Silver-containing Nanoparticles Research Articles

Analysis of Silver-containing Nanoparticles in Oysters Using Single-particle ICP-MS

Analysis of Silver-containing Nanoparticles in Oysters Using Single-particle ICP-MS

Uptake of Silver-Containing Nanoparticles in an Estuarine Plant: Speciation and Bioaccumulation.

Understanding the bioaccumulation of silver-containing nanoparticles (Ag-NPs) with different species, concentrations, and sizes in estuarine plants is critical to their related environmental risk. Herein, the distribution of Ag-NPs in tidewater, sediments, and plants (Scirpus triqueter) of field-constructed mesocosm was investigated, where tidewater was exposed to Ag0-NPs and Ag+ at environmentally relevant concentrations. Particle number concentrations (PNCs) and sizes of Ag-NPs with various species were analyzed using a multistep selective dissolution method followed by the single-particle- inductively coupled plasma mass spectrometry technique. After 30 days of exposure, more than half of Ag0-NPs were dissolved to Ag+ and about 1/4 of Ag+ were transformed into Ag0-/AgCl-NPs in tidewater. Ag-NPs in stems exposed to Ag0-NPs were found to be dominated by metallic Ag, while Ag+ exposure led to more Ag2S-NPs in stems. In roots, 71% and 51% of Ag-NPs were found as Ag2S-NPs for Ag0-NPs and Ag+ treatment groups, respectively. Plant stems had a significantly higher enrichment of Ag-NPs than roots. Based on both random forests and structure equation models, it is suggested that salinity of tidewater can regulate Ag0-NPs in tidewater indirectly by influencing AgCl-NPs in tidewater and further affect the total PNCs of Ag-NPs in plant stems. Moreover, elevated sulfate-reducing bacteria (SRB) result in more Ag2S-NPs in rhizosphere sediments, thereby enhancing the bioaccumulation of Ag-NPs by roots.

Investigating the behavior of ultratrace levels of nanoparticulate and ionic silver in a seawater mesocosm using single particle inductively coupled plasma – mass spectrometry

Silver nanoparticles (AgNPs) nowadays appear in close to 24% of consumer products that contain engineered nanomaterials. Thus, they are expected to be released into the environment, where their fate and effect are still undetermined. Considering the evidenced efficacy of the single particle Inductively Coupled Plasma – Mass Spectrometry (sp ICP-MS) technique in the study of nanomaterials, this work reports on the use of sp ICP-MS along with an online dilution sample introduction system for the direct analysis of untreated and spiked seawater samples, as part of a larger scale experiment studying the fate of Ag (ionic and nanoparticles) in seawater mesocosm systems. Silver nanoparticles coated with branched polyethyleneimine (BPEI@AgNPs) or ionic silver (Ag+) were introduced gradually into the seawater mesocosm tanks at very low, environmentally relevant concentrations (50 ng Ag L−1 per day, for 10 consecutive days, up to a total of 500 ng Ag L−1), and samples were collected and analyzed daily, within a consistent time window. Using very low detector dwell time (75 μs) and specialized data treatment, information was obtained on the nanoparticles’ size distribution and particle number concentration, as well as the ionic silver content, of both the AgNPs and the Ag+ treated seawater mesocosm tanks. The results for the AgNP treated samples indicated the rapid degradation of the added silver particles, and the subsequent increase of ionic silver, with recoveries close to 100% for the first days of the experiment. On the other hand, particle formation was observed in the Ag+ treated seawater tanks, and even though the number concentration of silver-containing nanoparticles increased throughout the experiment, the amount of silver per particle remained relatively constant from the early days of the experiment. In addition, the online dilution sample introduction system for the ICP-MS proved capable of handling the untreated seawater matrix without significant contamination issues and downtime, while the low dwell time and data treatment procedure developed were shown to be suitable for the analysis of nanomaterials at the low nm-scale, despite the complex and heavy matrix introduced into the ICP-MS.

Determination of the Particle Number Concentration, Size Distribution, and Species of Dominant Silver-Containing Nanoparticles in Soils by Single-Particle ICP-MS.

The potential risk of various silver-containing nanoparticles (AgCNPs) in soils is related to the concentration, size, and speciation, but their determination remains a great challenge. Herein, we developed an effective method for determining the particle number, size, and species of dominant AgCNPs in soils, including nanoparticles of silver (Ag NPs), silver chloride (AgCl NPs), and silver sulfide (Ag2S NPs). By ultrasonication wand-assisted tetrasodium pyrophosphate extraction, these AgCNPs were extracted efficiently from soils. Then, multistep selective dissolution of Ag NPs, AgCl NPs, and whole Ag NPs/AgCl NPs/Ag2S NPs was achieved by 1% (v/v) H2O2, 5% (v/v) NH3·H2O, and 10 mM thiourea in 2% (v/v) acetic acid, respectively. Finally, the particle number concentration and size distribution of AgCNPs in the extracts and the remaining AgCNP particle number concentration after each dissolution were determined by single-particle inductively coupled plasma mass spectroscopy for speciation of the dominant AgCNPs. AgCNPs were detected in all five soil samples with the concentrations of 0.23-8.00 × 107 particles/g and sizes of 16-110 nm. Ag2S NPs were the main form of AgCNPs in the examined soils with the percentage range of 53.98-69.19%, followed by AgCl NPs (11.42-23.31%) and Ag NPs (7.78-16.19%). Our method offers a new approach for evaluating the occurrence and potential risk of AgCNPs in environmental soils.

AuAg nanocomposites suppress biofilm-induced inflammation in human osteoblasts

Staphylococcus aureus (S. aureus) forms biofilm that causes periprosthetic joint infections and osteomyelitis (OM) which are the intractable health problems in clinics. The silver-containing nanoparticles (AgNPs) are antibacterial nanomaterials with less cytotoxicity than the classic Ag compounds. Likewise, gold nanoparticles (AuNPs) have also been demonstrated as excellent nanomaterials for medical applications. Previous studies have showed that both AgNPs and AuNPs have anti-microbial or anti-inflammatory properties. We have developed a novel green chemistry that could generate the AuAg nanocomposites, through the reduction of tannic acid (TNA). The bioactivity of the nanocomposites was investigated in S. aureus biofilm-exposed human osteoblast cells (hFOB1.19). The current synthesis method is a simple, low-cost, eco-friendly, and green chemistry approach. Our results showed that the AuAg nanocomposites were biocompatible with low cell toxicity, and did not induce cell apoptosis nor necrosis in hFOB1.19 cells. Moreover, AuAg nanocomposites could effectively inhibited the accumulation of reactive oxygen species (ROS) in mitochondria and in rest of cellular compartments after exposing to bacterial biofilm (by reducing 0.78, 0.77-fold in the cell and mitochondria, respectively). AuAg nanocomposites also suppressed ROS-triggered inflammatory protein expression via MAPKs and Akt pathways. The current data suggest that AuAg nanocomposites have the potential to be a good therapeutic agent in treating inflammation in bacteria-infected bone diseases.

Enhanced coagulation process for removing dissolved organic matter, microplastics, and silver nanoparticles

Dissolved organic carbon (DOC), microplastics (MPs), and silver nanoparticles (AgNPs) in water are of major concern because of their direct and indirect toxic effects on aquatic organisms and human exposure via water. This work investigated the effect of poly aluminum chloride (PACl) coagulation for reducing DOC, MPs, and AgNPs. This work used water from a canal in Thailand with a DOC of 5.2 mg/L in the experiment. AgNPs of 5–20 mg/L were added to canal water to create synthetic water for the PACl coagulation. Polyethylene and polypropylene (PP) type MPs were identified in the raw water with Fourier transform infrared spectroscopy. Coagulation with 15 mg/L of PACl performed better in the PP removal. The PACl coagulation at dosages of 15, 40, and 70 mg/L removed DOC by 16–20%, 44–52%, and 46–63% and AgNPs by 34–90%, 53–93%, and 81–95%, respectively. The presence of AgNPs at high levels could inhibit the efficiency of DOC reduction by the PACl coagulation. The FESEM identified the adsorption of silver-containing nanoparticles onto the flocs with increased dosages of PACl. So, PACl is a coagulant in the removal of AgNPs that can reduce health hazards and eco-toxicological risks in water sources due to the release of silver.

Sulfate-reducing bacteria (SRB) can enhance the uptake of silver-containing nanoparticles by a wetland plant

The enhanced phyto-uptake of Ag-NPs in the presence of SRB, by transforming Ag0-NPs into secondary Ag sulfide-NPs.

Spatiotemporal distribution of silver and silver-containing nanoparticles in a prealpine lake in relation to the discharge from a wastewater treatment plant

Over two years we assessed silver-containing nanoparticles (SCN) and total silver in the in- and effluent of a wastewater treatment plant (WWTP) discharging purified wastewater into a lake. Additionally, total silver was measured in sludge of the WWTP and in water, sediment, and fish of the receiving lake at several points with varying distance to the discharge point and compared to a reference lake. We used a novel single particle inductively coupled plasma mass spectrometry (SP-ICP-MS, with microsecond time resolution) protocol to detect SCN in environmental samples in addition to total elemental analysis by ICP-MS/OES (optical emission spectrometry), and histological analysis by dark-field microscopy. Total silver was below the limit of quantification in the WWTP influent and effluent, and in lake water and fishes, except for one influent sample. However, comparably high silver concentrations were detected in the sludge, irrespective of the season, indicating accumulation of silver. Furthermore, SP-ICP-MS analysis of influent samples confirmed the presence of SCN. Despite the high removal efficiency of silver and SCN from the wastewater, high silver concentrations were measured in the sediment near the discharge point, suggesting a constant silver input into the lake. Silver and SCN levels were lower than concentrations leading to adverse effects in recently published toxicological studies, thus the investigated lake ecosystem is currently not at risk.

Discerning the Sources of Silver Nanoparticle in a Terrestrial Food Chain by Stable Isotope Tracer Technique.

The increasing use of silver-containing nanoparticles (NPs) in commercial products has led to NP accumulation in the environment and potentially in food webs. Identifying the uptake pathways of different chemical species of NPs, such as Ag2S-NP and metallic AgNPs, into plants is important to understanding their entry into food chains. In this study, soybean Glycine max L. was hydroponically exposed to Ag2S-NPs via their roots (10-50 mg L-1) and stable-isotope-enriched 109AgNPs via their leaves [7.9 μg (g fresh weight)-1]. Less than 29% of Ag in treated leaves (in direct contact with 109AgNP) was accumulated from root uptake of Ag2S-NPs, whereas almost all of the Ag in soybean roots and untreated leaves sourced from Ag2S-NPs. Therefore, Ag2S-NPs are phytoavailable and translocate upward. During trophic transfer the Ag isotope signature was preserved, indicating that accumulated Ag in snails most likely originated from Ag2S-NPs. On average, 78% of the Ag in the untreated leaves was assimilated by snails, reinforcing the considerable trophic availability of Ag2S-NPs via root uptake. By highlighting the importance of root uptake of Ag2S-NPs in plant uptake and trophic transfer to herbivores, our study advances current understanding of the biogeochemical fate of Ag-containing NPs in the terrestrial environment.

Physicochemical characterization of aerosol particles emitted by electrical appliances

Adverse health effects of airborne particulate matter depend on parameters like particle size, particle surface and chemical composition. Major emission of indoor particles is caused by combustion processes like tobacco smoking and cooking. Nevertheless, the use of household electrical appliances, such as vacuum cleaners, flat irons or hair dryers, can produce particles as well.In this study the emissions of different hair dryers and flat irons were investigated using a test chamber. The particle number concentrations, particle volume concentrations, as well as the size distributions were measured. Particles were sampled and analyzed by electron microscopy, inductively coupled plasma mass spectrometry and gas chromatography mass spectrometry. Moreover different volatile organic compounds (VOCs) were measured.Each tested appliance, especially flat irons produced small particles with diameters far below 100nm and might be a nonnegligible source for indoor particles. Copper was the main identified element in most of the particles emitted from hair dryers, but in the emission of two hair dryers silver-containing nanoparticles were found as well. Various VOCs were observed in the emission of both flat irons and hair dryers, while cyclic siloxanes were detected only in the emission of flat irons. The use of flat irons or hair dryers may significantly contribute to the personal particle exposure.

Characterization of engineered nanoparticles in commercially available spray disinfectant products advertised to contain colloidal silver

Given the potential for human exposure to silver nanoparticles from spray disinfectants and dietary supplements, we characterized the silver-containing nanoparticles in 22 commercial products that advertised the use of silver or colloidal silver as the active ingredient. Characterization parameters included: total silver, fractionated silver (particulate and dissolved), primary particle size distribution, hydrodynamic diameter, particle number, and plasmon resonance absorbance. A high degree of variability between claimed and measured values for total silver was observed. Only 7 of the products showed total silver concentrations within 20% of their nominally reported values. In addition, significant variations in the relative percentages of particulate vs. soluble silver were also measured in many of these products reporting to be colloidal. Primary silver particle size distributions by transmission electron microscopy (TEM) showed two populations of particles - smaller particles (<5nm) and larger particles between 20 and 40nm. Hydrodynamic diameter measurements using nanoparticle tracking analysis (NTA) correlated well with TEM analysis for the larger particles. Z-average (Z-Avg) values measured using dynamic light scattering (DLS); however, were typically larger than both NTA or TEM particle diameters. Plasmon resonance absorbance signatures (peak absorbance at around 400nm indicative of metallic silver nanoparticles) were only noted in 4 of the 9 yellow-brown colored suspensions. Although the total silver concentrations were variable among products, ranging from 0.54mg/L to 960mg/L, silver containing nanoparticles were identified in all of the product suspensions by TEM.

Synthesis and Bioactivity of RGO/TiO&lt;sub&gt;2&lt;/sub&gt;-Noble Metal Nanocomposite Flakes

This study aims to describe the influence of adding graphene oxide to TiO2-noble metal (Me=Ag, Au or Pd) composite nanoparticles on their bioactivity (formation of RGO/TiO2-Me nanocomposite system). The obtained nanocomposite flakes and reference TiO2-Me nanoparticles were characterized using SEM, HRTEM and XPS spectroscopy, N2 sorption analysis and helium pycnometer. The analysis of the antibacterial properties of synthesized nanocomposites revealed a growth inhibiting effect of TiO2-Ag particles on gram positive bacteria such as: Staphylococcus aureus, Sarcina lutea and Bacillus subtilis. In the case of nanocomposite flakes containing RGO the visible changes in bacteriostatic properties were observed, including unexpected reversal of the antimicrobial activity of silver-containing nanoparticles into the stimulation of growth of applied bacterial strains. The stimulation of growth was not observed for TiO2-Au and Pd nanoparticles deposited on the surface of RGO.

Highly Efficient Removal of Silver-Containing Nanoparticles in Waters by Aged Iron Oxide Magnetic Particles

Methods for the removal of silver nanoparticles (AgNPs) and their transformation products, silver-containing nanoparticles (AgCNPs), are important, because of their potential risks to the general population and the environment. In this study, aged iron oxide magnetic particles (IOMPs) were synthesized by a simple solvothermal reaction and used for the removal of AgCNPs. The prepared IOMPs exhibit a high adsorption capacity toward AgCNPs in aqueous medium. Kinetic studies indicated that the adsorption of AgCNPs is a pseudo-second-order process. The experimental data for the adsorption of AgCNPs follow the Langmuir isotherm model, and their maximum adsorption capacities were 19.9–62.8 mg/g at pH 6.2 and 298 K. The sorption mean free energy calculated by the Dubinin–Radushkevich isotherm was 4.09–5.17 kJ/mol, indicating the occurrence of physisorption, which was mainly due to the electrostatic interactions. The IOMP adsorbents maintained high removal efficiencies after four cycles of adsorption–desorption, s...

Three-Dimensional Nanostructures with Biocidal Activity Created on a Siloxane-Containing Copolyimide Film

Surface morphological characteristics of a copolyimide film prepared from a fluorine-based dianhydride combined with an aliphatic siloxane-based diamine and an aromatic containing ether linkages one, were studied before and after oxigen plasma treatment using atomic force microscopy (AFM). The three-dimensional texture parameters calculated from the AFM data have highlighted a more pronounced surface morphology (higher average roughness and developed interfacial area ratio), improved bearing properties and no predominant orientation, as the plasma exposure time was increased from 6 to 10 minutes, using the same power (40 W). The reactive groups generated on the binding surface have facilitated the interaction with a biocidal agent, such as silver nitrate. This creates silver-containing nanoparticles, of about 120-150 nm, uniformly distributed on the copolymer surface, with a density of 10±2 particles/μm2. The functionalization with the biocidal agent of the flourinated copolyimide surface was conducted for testing its antimicrobial properties, namely the inhibition/destruction of Escherichia coli bacterium.

Rapid chromatographic separation of dissoluble Ag(I) and silver-containing nanoparticles of 1-100 nanometer in antibacterial products and environmental waters.

Sensitive and rapid methods for speciation analysis of nanoparticulate Ag (NAg) and Ag(I) in complex matrices are urgently needed for understanding the environmental effects and biological toxicity of silver nanoparticles (AgNPs). Herein we report the development of a universal liquid chromatography (LC) method for rapid and high resolution separation of dissoluble Ag(I) from nanoparticles covering the entire range of 1-100 nm in 5 min. By using a 500 Å poresize amino column, and an aqueous mobile phase containing 0.1% (v/v) FL-70 (a surfactant) and 2 mM Na2S2O3 at a flow rate of 0.7 mL/min, all the nanoparticles of various species such as Ag and Ag2S were eluted in one fraction, while dissoluble Ag(I) was eluted as a baseline separated peak. The dissoluble Ag(I) was quantified by the online coupled ICP-MS with a detection limit of 0.019 μg/L. The NAg was quantified by subtracting the dissoluble Ag(I) from the total Ag content, which was determined by ICP-MS after digestion of the sample without LC separation. While the addition of FL-70 and Na2S2O3 into the mobile phase is essential to elute NAg and Ag(I) from the column, the use of 500 Å poresize column is the key to baseline separation of Ag(I) from ∼ 1 nm AgNPs. The feasibility of the proposed method was demonstrated in speciation analysis of dissoluble Ag(I) and NAg in antibacterial products and environmental waters, with very good chromatographic repeatability (relative standard deviations) in both peak area (<2%) and retention time (<0.6%), excellent spiked recoveries in the range of 84.7-102.7% for Ag(I) and 81.3-106.3% for NAg. Our work offers a novel approach to rapid and baseline separation of dissoluble metal ions from their nanoparticulate counterparts covering the whole range of 1-100 nm.

Mechanisms and kinetics of short pulse laser-induced destruction of silver-containing nanoparticles in multicomponent silicate photo-thermo-refractive glass.

Photo-thermo-refractive (PTR) glass is a photosensitive multi-component silicate glass that is commercially used for the recording of volume holographic elements and finds many applications in advanced laser systems. Refractive index decrement in this glass is observed after UV exposure followed by thermal development. This procedure also causes the appearance of Ag-containing particles that can then be optically bleached by using the second harmonic of a Nd:YAG laser. Despite the broad usage of this method, its mechanisms are still unclear. In this paper, a systematic study of the short pulse laser-induced destruction of Ag-containing particles' kinetics versus incident energy per pulse and dosage is presented. We show that no bleaching of Ag-containing particles occurs for an energy density in laser pulses below 0.1 J/cm2 while above 1 J/cm2, the efficiency of bleaching saturates. Efficiency of bleaching depends on the type of particles to be bleached (Ag, AgBr…). Using a simple model of short pulse laser interaction with nanoparticles embedded in glass, the temperature of the Ag-containing particles reached during the laser interaction is shown to be large enough to produce complete dissipation of these particles which is expected to be the main mechanism of short pulse laser-induced destruction of Ag-containing particles.

Removal of silver nanoparticles by coagulation processes

Commercial use of silver nanoparticles (AgNPs) will lead to a potential route for human exposure via potable water. Coagulation followed by sedimentation, as a conventional technique in the drinking water treatment facilities, may become an important barrier to prevent human from AgNP exposures. This study investigated the removal of AgNP suspensions by four regular coagulants. In the aluminum sulfate and ferric chloride coagulation systems, the water parameters slightly affected the AgNP removal. However, in the poly aluminum chloride and polyferric sulfate coagulation systems, the optimal removal efficiencies were achieved at pH 7.5, while higher or lower of pH could reduce the AgNP removal. Besides, the increasing natural organic matter (NOM) would reduce the AgNP removal, while Ca2+ and suspended solids concentrations would also affect the AgNP removal. In addition, results from the transmission electron microscopy and X-ray diffraction showed AgNPs or silver-containing nanoparticles were adsorbed onto the flocs. Finally, natural water samples were used to validate AgNP removal by coagulation. This study suggests that in the case of release of AgNPs into the source water, the traditional water treatment process, coagulation/sedimentation, can remove AgNPs and minimize the silver ion concentration under the well-optimized conditions.

Speciation of Silver Nanoparticles and Silver(I) by Reversed-Phase Liquid Chromatography Coupled to ICPMS

The tremendous increase in the use of engineered nanoparticles in daily life has raised concerns about their impact on the environment and in biological systems. Among them, silver-containing material is of high industrial interest and of manifold use in consumer products, mainly because of their antimicrobial activity. Therefore, analytical methods are urgently needed for the reliable determination of Ag nanoparticles and their corresponding Ag(I) species. In this study, we present the development of coupling reversed-phase high-performance liquid chromatography (HPLC) to inductively coupled plasma-mass spectrometry (ICPMS) for the speciation of engineered Ag-containing nanoparticles and Ag(I) species. The method has been designed for the separation/detection of all investigated silver species in a single chromatographic run. For this purpose, the addition of thiosulfate to the mobile phase has been used to elute Ag(I) species from the column without degradation of the other species. The analytical figures of merit show repeatable results for the recoveries (>80%) of both, the Ag nanoparticles and Ag(I) species. The obtained detection limits are in the medium ng·L(-1) range and therefore allow the trace analysis of the sought analytes in real samples. However, the matrix (e.g., fetal bovine serum) showed an impact on the retention behavior of the Ag nanoparticles, so that for size determinations the use of gold nanoparticles as internal size standard is suggested. Finally, the analysis of textile products exemplarily demonstrates the applicability to the analysis of real samples. Besides silver-containing nanoparticles, Ag(I) species can be identified as one of the major species in the extraction solution from sports socks. However, extraction conditions will be the subject of further investigations in the future in order to obtain reliable quantitative data.

A Preliminary Assessment of Silver Nanoparticle Inhibition of Monkeypox Virus Plaque Formation

The use of nanotechnology and nanomaterials in medical research is growing. Silver-containing nanoparticles have previously demonstrated antimicrobial efficacy against bacteria and viral particles. This preliminary study utilized an in vitro approach to evaluate the ability of silver-based nanoparticles to inhibit infectivity of the biological select agent, monkeypox virus (MPV). Nanoparticles (10–80 nm, with or without polysaccharide coating), or silver nitrate (AgNO3) at concentrations of 100, 50, 25, and 12.5 μg/mL were evaluated for efficacy using a plaque reduction assay. Both Ag-PS-25 (polysaccharide-coated, 25 nm) and Ag-NP-55 (non-coated, 55 nm) exhibited a significant (P ≤ 0.05) dose-dependent effect of test compound concentration on the mean number of plaque-forming units (PFU). All concentrations of silver nitrate (except 100 μg/mL) and Ag-PS-10 promoted significant (P ≤ 0.05) decreases in the number of observed PFU compared to untreated controls. Some nanoparticle treatments led to increased MPV PFU ranging from 1.04- to 1.8-fold above controls. No cytotoxicity (Vero cell monolayer sloughing) was caused by any test compound, except 100 μg/mL AgNO3. These results demonstrate that silver-based nanoparticles of approximately 10 nm inhibit MPV infection in vitro, supporting their potential use as an anti-viral therapeutic.