Dissolution Of Ag Nanoparticles Research Articles

Single-Particle Electrochemical Imaging Provides Insights into Silver Nanoparticle Dissolution at the Solution-Solid Interface.

Dissolution of nanoparticles is an environmental interfacial process that affects the transformation of nanoparticles. Understanding the dissolution processes of nanoparticles is important to predict their fate in the aquatic environment. However, studying nanoparticle dissolution kinetics is still challenging since dissolution is usually coupled with nanoparticle aggregation. Here, we probed the dissolution process of Ag nanoparticles at the single-particle level by surface plasmon resonance microscopy. The single-particle imaging capability enabled us to classify Ag nanoparticles, measure the dissolution dynamics of single nanoparticles, and correlate the aggregation size with oxidation activity. Moreover, we studied the dual effect of natural organic matter on the dissolution of Ag nanoparticles and validated this result with real natural freshwater. Our study provides new insights into the dissolution of Ag nanoparticles, and this technique can be extended for other nanomaterials to evaluate their fate in aquatic environments.

Effects of rice root exudates on aggregation, dissolution and bioaccumulation of differently-charged Ag nanoparticles.

The biological toxicity and eco-environmental risk of metal nanoparticles (MNPs) is closely related to their stability. The stability of MNPs not only depends on their own properties but also on the effects of biological and environmental factors. To better understand the interaction between biological factors and MNPs in aquatic environments, the effects of total rice root exudates (T-RRE) on the aggregation, dissolution and bioaccumulation of Ag nanoparticles (AgNPs) with different surface charges were investigated in detail. Results indicated that T-RRE can induce the aggregation and sedimentation, and hinder the dissolution of polyethyleneimine-coated AgNPs (AgNPs@PEI) with positive surface charges as well as reducing the bioaccumulation of Ag in rice roots. T-RRE had no obvious effect on the dispersion stability of AgNPs@Cit (negatively charged citrate-coated AgNPs) and AgNPs@PVP (near electrically neutral polyvinylpyrrolidone-coated AgNPs), although T-RRE could induce the dissolution of AgNPs@Cit and AgNPs@PVP. In the molecular fractions of T-RRE, high-molecular-weight root exudates (H-RRE) play a key role in inducing the aggregation of AgNPs@PEI and hindering the bioaccumulation of Ag in rice roots. Compared with H-RRE, low-molecular-weight root exudates (L-RRE) can promote the dissolution of AgNPs@Cit and AgNPs@PVP, but it can obviously promote silver accumulation in rice roots. The difference in charge intensity between L-RRE and T-RRE plays a key role in inducing the aggregation and dissolution of AgNPs with different charges. These findings provide a foundation for investigation of the interactions between rice root exudates and nanoparticles with different surface charges in complex environmental systems.

Dissolution of Ag Nanoparticles in Agricultural Soils and Effects on Soil Exoenzyme Activities

To assess environmental risks related to the mobility and toxicity of AgNPs, the chemical availability of AgNPs and polyvinylpyrrolidone-coated AgNPs (PVP-AgNPs) in three agricultural soils was quantified in a pot experiment. Porewater collection and soil extractions with 0.01 M CaCl2, 0.4 M Glycine (pH 1.5) and 0.05 M NH4-EDTA were performed. The effect on soil exoenzyme activities was also assessed. Porewater concentration was low (<0.4% and <0.04% of dosed Ag, for AgNPs and PVP-AgNPs, respectively) and only detected in acidic soils (pH 4.4 and 4.9). The PVP-coating reduced the downward mobility of AgNPs in soil and possibly also their dissolution rate (and subsequent release of dissolved Ag+ ions into porewater). The effect of variation in organic matter on soil enzymatic activity was larger than that of AgNPs, as no significant additional inhibitory effect from Ag could be observed. Only at low pH and in the presence of complexing ligands that form very stable Ag complexes (0.4 M Glycine extraction at pH 1.5) up to 58% of the Ag added to soil was released (independently of PVP coating). An extraction with glycine is proposed as a useful indicator of potentially available Ag in soils.

Controlled Tuning of the Size of Ag-Hydrosol Nanoparticles by Nonstabilized THF and Detection of Peroxides in THF.

Surface plasmon extinction (SPE) spectra of plasmonic nanoparticles (NPs) are sensitive indicators of their composition, size, shape, interparticle interactions, and of the dielectric constant of their ambient. In this study, rapid changes in SPE spectra of Ag NPs suggesting variations in NP size and concentration were detected after addition of aged tetrahydrofuran (THF). Using time-dependent UV/vis spectroscopy combined with factor analysis, transmissionelectron microscopy imaging, selected-area electron diffraction, and energy-dispersive X-ray analysis, we observed that an over-limit amount of aged THF fully dissolved Ag NPs with no plasmon recovery. By contrast, an under-limit amount led to incomplete dissolution of Ag NPs and, after reaching the turnover point, to spontaneous recrystallization on residual Ag nuclei, as demonstrated by the SPE band intensity recovery to the original or even higher values. The newly formed Ag NPs were isometric, and their diameter was dependent on the added amount of THF. Furthermore, both Ag NP dissolution and recrystallization were caused by THF peroxides and their reduction products. Therefore, the dissolution of Ag NPs and the resulting hydrosol bleaching may be used as an indicator of the presence of peroxides in THF. Moreover, the reaction of aged THF with Ag NPs can be employed as a tool for tuning the size of Ag NPs in hydrosols.

A non-enzyme cascade amplification strategy for colorimetric assay of disease biomarkers.

A non-enzyme cascade amplification strategy, based on the dissolution of Ag nanoparticles and a Pt nanocube-catalyzed reaction, for colorimetric assay of disease biomarkers was developed. This strategy overcomes the intrinsic limitations of enzymes involved in conventional enzymatic amplification techniques, thanks to the utilization of noble-metal nanostructures with superior properties.

Physicochemical transformation and algal toxicity of engineered nanoparticles in surface water samples

Most studies on the behavior and toxicity of engineered nanoparticles (NPs) have been conducted in artificial water with well-controlled conditions, which are dramatically different from natural waters with complex compositions. To better understand the fate and toxicity of NPs in the natural water environment, physicochemical transformations of four NPs (TiO2, ZnO, Ag, and carbon nanotubes (CNTs)) and their toxicities towards a unicellular green alga (Chlorella pyrenoidosa) in four fresh water and one seawater sample were investigated. Results indicated that water chemistry had profound effects on aggregation, dissolution, and algal toxicity of the NPs. The strongest homoaggregation of the NPs was associated with the highest ionic strength, but no obvious correlation was observed between the homoaggregation of NPs and pH or dissolved organic matter content of the water samples. The greatest dissolution of ZnO NPs also occurred in seawater with the highest ionic strength, while the dissolution of Ag NPs varied differently from ZnO NPs. The released Zn2+ and especially Ag+ mainly accounted for the algal toxicity of ZnO and Ag NPs, respectively. The NP-cell heteroagglomeration occurred generally for CNTs and Ag NPs, which contributed to the observed nanotoxicity. However, there was no significant correlation between the observed nanotoxicity and the type of NP or the water chemistry. It was thus concluded that the physicochemical transformations and algal toxicities of NPs in the natural water samples were caused by the combined effects of complex water quality parameters rather than any single influencing factor alone. These results will increase our knowledge on the fate and effects of NPs in the aquatic environment.

Phytotoxicity of silver nanoparticles to cucumber (Cucumis sativus) and wheat (Triticum aestivum)

The increasing release of silver (Ag) nanoparticles (NPs) into the environment highlights the importance of exploring the interactions between Ag NPs and plants, which are the basis of most ecosystems. In this study, two plant species, Cucumis sativus L. (cucumber) and Triticum aestivum L. (wheat) were exposed to Ag NPs and Ag+ (added as AgNO3) at the germination and vegetative growth stages. Above certain concentrations, Ag NPs and Ag+ were toxic to the two plants. However, stimulatory effects were observed on root elongation for the cucumbers that were exposed to Ag NPs at concentrations below 200 mg/L, and Ag+ at concentrations below 5 mg/L. The two plants were more susceptible to the toxicity of Ag NPs at the vegetative growth stage than the germination stage. Ag was accumulated in the roots and was subsequently translocated to the shoots after the exposure to Ag NPs. To assess the role of released Ag+, we measured the dissolution of Ag NPs in exposure solutions. About 0.03% and 0.01% of Ag NPs were dissolved into a hydroponic solution at the germination stage for cucumber and wheat, respectively; while 0.17% and 0.06% at the vegetative period for cucumber and wheat, respectively. Cysteine, a strong chelating ligand of Ag+, could completely eliminate the effects of Ag NPs on cucumber and wheat, suggesting that the phytotoxicity of Ag NPs was possibly caused by the release of Ag+.

Aqueous route to facile, efficient and functional silica coating of metal nanoparticles at room temperature.

Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also applied to prepare highly surface-enhanced Raman scattering (SERS)-active Ag@SiO2-SH NPs with different types of Raman molecules for highly sensitive SERS-based applications in various fields.

The Effects of Sedimentation and Dissolution on the Cytotoxicity of Ag Nanoparticles

Nanoparticles (NPs) are being employed for various industrial purposes with increasing frequency, yet the adverse health effects associated with the prolonged exposure of humans and the environment to NPs has not been well-established. Particularly, the effects of the extrinsic (or dynamic) physicochemical properties of NPs in aqueous cell culture media (e.g., hydrodynamic size, aggregation, agglomeration, sedimentation, and dissolution of nanoparticles) on the cytotoxicities of the NPs are barely understood. In this study, to investigate the effects of two important extrinsic properties of Ag NPs, namely the sedimentation and dissolution of Ag NPs, we performed MTT cell viability tests for HeLa cells exposed to Ag NPs with varying extrinsic properties. Ag NPs with different hydrodynamic sizes, sedimentation rates, and dissolution rates were prepared via exposure to NaCl and FBS. Sedimentation of aggregated/agglomerated Ag NPs was found to contribute more significantly to the cytotoxicity of Ag NPs during early periods of exposure, whereas the cytotoxicity was more greatly enhanced later during the exposure period due to the increase in silver ions. Therefore, it is offered that any assessment of NP cytotoxicity should consider the extrinsic properties of NPs, and their time-dependent properties, because the dominant processes affecting NP cytotoxicity may change over time and lead to a misunderstanding or poor prediction of NP cytotoxicity.

Short-term molecular-level effects of silver nanoparticle exposure on the earthworm, Eisenia fetida

Short-term changes in levels of expression of nine stress response genes and oxidative damage of proteins were examined in Eisenia fetida exposed to polyvinylpyrrolidone (PVP) coated Ag nanoparticles (Ag-NP) and AgNO3 in natural soils. The responses varied significantly among days with the highest number of significant changes occurring on day three. Similarity in gene expression patterns between Ag-NPs and AgNO3 and significant relationships of expression of CAT and HSP70 with Ag soil concentration suggest similarity in toxicity mechanisms of Ag ions and NPs. Significant increases in the levels of protein carbonyls on day three of the exposure to both ions and Ag-NPs indicate that both treatments induced oxidative stress. Our results suggest that Ag ions drive short term toxicity of Ag-NPs in E. fetida. However, given that <15% of Ag in the NPs was oxidized in these soils, dissolution of Ag-NPs is likely to occur after or during their uptake.

Revealing oxidation kinetics of dielectric-embedded Ag nanoparticles via in situ optical microspectroscopy

The oxidation kinetics of Ag nanoparticles (NPs) embedded in an aluminum oxide film deposited on quartz have been assessed via an in situ real-time monitoring of plasmonic evolution during thermal processing in air. A temperature-dependent exponential decay in the peak intensity of Ag NPs’ absorption was revealed, which was analyzed through first-order kinetics. An activation energy of 3.28 (±0.27)×104Jmol−1 was estimated in good agreement with the oxidative dissolution of similar-sized Ag NPs in liquid phase reported by Ho et al. [11]. Results are discussed in the context of mechanistic parallelisms and physico-chemical interactions in the air-atmosphere/nanocomposite-film/substrate system.

Size-dependent photochromism-based holographic storage of Ag/TiO2 nanocomposite film

The influence of size distribution of Ag nanoparticles (NPs) on photochromic behavior and holographic storage dynamics of Ag/TiO2 films was investigated using a 532 nm laser as excitation source and recording beams, respectively. Experimental results suggest that small Ag NPs are subject to easier photoinduced oxidative dissolution than large Ag NPs under the 532 nm excitation, and contribute to the rapid growth of holographic grating in the initial stage. These observations were discussed in terms of size-dependent silver redox potential influencing both interfacial electron transfer among Ag NPs and TiO2 matrix and subsequent dissolution of Ag NPs, as well as surface plasmon resonance absorption property of Ag NPs also related to their size distribution.