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Sulfidation of silver nanowires inside human alveolar epithelial cells: a potential detoxification mechanism.

ABSTRACT: Silver nanowires (AgNWs) are being developed for use in optoelectronics. However before widespread usage, it is crucial to determine their potential effects on human health. It is accepted that Ag nanoparticles (AgNPs) exert toxic effects by releasing Ag(+) ions, but much less is known about whether Ag(+) reacts with compounds, or any downstream bioactive effects of transformed AgNPs. Analytical high-resolution transmission electron microscopy has been employed to elucidate cellular uptake and reactivity of AgNWs inside human alveolar epithelial type 1-like cells. AgNWs were observed in the cytoplasm and membrane-bound vesicles, and precipitation of Ag2S within the cell occurred after 1 h exposure. Cell viability studies showed no evidence of cytotoxicity and reactive oxygen species were not observed on exposure of cells to AgNWs. We suggest that Ag2S formation acts as a 'trap' for free Ag(+), significantly limiting short-term toxicological effects - with important consequences for the safety of Ag-nanomaterials to human health.

SUBMITTER: Chen S

PROVIDER: S-EPMC4337028 | biostudies-literature | 2013 Oct

REPOSITORIES: biostudies-literature

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Sulfidation of silver nanowires inside human alveolar epithelial cells: a potential detoxification mechanism.

Chen Shu S Goode Angela E AE Sweeney Sinbad S Theodorou Ioannis G IG Thorley Andrew J AJ Ruenraroengsak Pakatip P Chang Yan Y Gow Andrew A Schwander Stephan S Skepper Jeremy J Zhang Junfeng Jim JJ Shaffer Milo S MS Chung Kian Fan KF Tetley Teresa D TD Ryan Mary P MP Porter Alexandra E AE

Nanoscale 20131001 20

Silver nanowires (AgNWs) are being developed for use in optoelectronics. However before widespread usage, it is crucial to determine their potential effects on human health. It is accepted that Ag nanoparticles (AgNPs) exert toxic effects by releasing Ag(+) ions, but much less is known about whether Ag(+) reacts with compounds, or any downstream bioactive effects of transformed AgNPs. Analytical high-resolution transmission electron microscopy has been employed to elucidate cellular uptake and r ...[more]

PMID: 23970174

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Project description:Background: The toxicity of inhaled silver nanoparticles on contractile and pro-inflammatory airway smooth muscle cells (ASMCs) that control airway calibre is unknown. We explored the oxidative activities and sulfidation processes of the toxic-inflammatory response. Method: Silver nanospheres (AgNSs) of 20 nm and 50 nm diameter and silver nanowires (AgNWs), short S-AgNWs, 1.5 μm and long L-AgNWs, 10 μm, both 72 nm in diameter were manufactured. We measured their effects on cell proliferation, mitochondrial reactive oxygen species (ROS) release and membrane potential, and also performed electron microscopic studies. Main results and findings: The greatest effects were observed for the smallest particles with the highest specific surface area and greatest solubility that were avidly internalised. ASMCs exposed to 20 nm AgNSs (25 μg mL-1) for 72 hours exhibited a significant decrease in DNA incorporation (-72.4%; p < 0.05), whereas neither the 50 nm AgNSs nor the s-AgNWs altered DNA synthesis or viability. There was a small reduction in ASMC proliferation for the smaller AgNS, although Ag+ at 25 μL mL-1 reduced DNA synthesis by 93.3% (p < 0.001). Mitochondrial potential was reduced by both Ag+ (25 μg mL-1) by 47.1% and 20 nm Ag NSs (25 μg mL-1) by 40.1% (*both at p < 0.05), but was not affected by 50 nm AgNSs and the AgNWs. None of the samples showed a change in ROS toxicity. However, malondialdehyde release, associated with greater total ROS, was observed for all AgNPs, to an extent following the geometric size (20 nm AgNS: 213%, p < 0.01; 50 nm AgNS: 179.5%, p < 0.01 and L-AgNWs by 156.2%, p < 0.05). The antioxidant, N-acetylcysteine, prevented the reduction in mitochondrial potential caused by 20 nm AgNSs. The smaller nanostructures were internalised and dissolved within the ASMCs with the formation of non-reactive silver sulphide (Ag2S) on their surface, but with very little uptake of L-AgNWs. When ASMCs were incubated with H2S-producing enzyme inhibitors, the spatial extent of Ag2S formation was much greater. Conclusion: The intracellular toxicity of AgNPs in ASMCs is determined by the solubility of Ag+ released and the sulfidation process, effects related to particle size and geometry. Passivation through sulfidation driven by biogenic H2S can outcompete dissolution, thus reducing the toxicity of the smaller intracellular Ag nanostructures.

Project description:Understanding the structure transformation of engineered nanomaterials (ENMs) is a grand measurement challenge, which impacts many aspects of ENMs applications, such as their efficacy, safety, and environmental consequence. To address the significant knowledge gap regarding the fundamental kinetic rate and extent of ENM transformation in the environment, we present a comprehensive and mechanistic structural investigation of the transformation, aggregation, and dissolution behavior of a polyvinylpyrrolidone-coated silver nanoparticle (AgNP) suspension upon sulfidation in moderately reduced hard water with fulvic acid and dissolved Na2S. This reaction is among the most prevalent and industrially and environmentally relevant ENMs transformation. Using ex situ transmission electron microscopy (TEM) and both in situ and ex situ synchrotron-based small angle X-ray scattering (SAXS) and X-ray diffraction (XRD), we find that sulfidation of faceted AgNPs strongly depends on the crystallographic orientation of the facets, with nanometer-scale passivation layers developed on {111} and {100} facets and continuous nucleation and growth on {110} facets. Nanobeam electron diffraction and atomic resolution imaging show Ag and Ag2S domains both possess a high degree of crystalline order, contradicting amorphous structures as previously reported. In situ SAXS/XRD allowed simultaneous determination of the morphological changes and extent of sulfidation of AgNPs. SAXS/XRD results strongly indicate sulfidation follows first-order reaction kinetics without any aggregation. Aided by their size monodispersity, for the first time, using direct, in situ morphology and atomic-structure probes whose results mutually corroborate, we unequivocally determined the sulfidation rate constant of AgNPs under an environmentally relevant condition (~0.013 min-1 for 68 nm diameter AgNPs). A rigorous analysis of the long-term sulfidation product of the AgNPs under different S/Ag ratios using ex situ SAXS/XRD clearly demonstrates that the silver mass in the original AgNP and transformed Ag/Ag2S NP is preserved. This result has important environmental implications, strongly suggesting that Ag+ ions, a known highly effective antimicrobial agent, are not leached into the solution during sulfidation of AgNPs. The combined nondestructive methodology can be extended to unfold the structure transformation pathway and kinetics in a broad range of ENM systems.

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Sulfidation of silver nanowires inside human alveolar epithelial cells: a potential detoxification mechanism.

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Sulfidation of silver nanowires inside human alveolar epithelial cells: a potential detoxification mechanism.

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