Xiaoxia Zhou

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.

Fabrication of a Au Nanoporous Film by Self-Organization of Networked Ultrathin Nanowires and Its Application as a Surface-Enhanced Raman Scattering Substrate for Single-Molecule Detection

Due to its demonstrated usefulness in fields such as trace analysis, biodiagnosis, and in vivo study, surface-enhanced Raman scattering (SERS) has received renewed interest in recent years. Development of SERS substrates is of great importance as the SERS intensity and reproducibility depend strongly on the SERS substrates. In this paper we report the fabrication of Au nanoporous film (NPFs) by self-organization of networked ultrathin Au nanowires for use as SERS substrates. The acquired Au NPFs display controllable thickness, low relative density, and considerable specific surface area. Furthermore, this self-organization of nanowires not only provides abundant junctions between nanowires, 5-20 nm nanopores, and three-dimensional nanowells, but also makes nanopores/nanogaps down to 1-2 nm. These nanoscale characteristics result in a high spatial density of hotspots with Raman enhancement factors up to 10(9). Combined with the uniformity and high purity, our Au NPF provides high-quality substrates for SERS sensing.

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV-visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV-visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca(2+) and Mg(2+)) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.

Exposure Medium: Key in Identifying Free Ag + as the Exclusive Species of Silver Nanoparticles with Acute Toxicity to Daphnia magna

It is still not very clear what roles the various Ag species play in the toxicity of silver nanoparticles (AgNPs). In this study, we found that traditional exposure media result in uncontrollable but consistent physicochemical transformation of AgNPs, causing artifacts in determination of median lethal concentration (LC50) and hindering the identification of Ag species responsible for the acute toxicity of AgNPs to Daphnia magna. This obstacle was overcome by using 8 h exposure in 0.1 mmol L−1 NaNO3 medium, in which we measured the 8-h LC50 of seven AgNPs with different sizes and coatings, and determined the concentrations of various Ag species. The LC50 as free Ag+ of the seven AgNPs (0.37–0.44 μg L−1) agreed very well with that of AgNO3 (0.40 μg L−1), and showed the lowest value compared to that as total Ag, total Ag+, and dissolved Ag, demonstrating free Ag+ is exclusively responsible for the acute toxicity of AgNPs to D. magna, while other Ag species in AgNPs have no contribution to the acute toxicity. Our results demonstrated the great importance of developing appropriate exposure media for evaluating risk of nanomaterials.

Cysteine modified small ligament Au nanoporous film: an easy fabricating and highly efficient surface-assisted laser desorption/ionization substrate.

Au nanoporous films (NPFs) with different surface modification and morphology were fabricated and utilized as substrates for the analysis of a series of compounds, including amino acids, drug, cyclodextrins, peptides, and polyethylene glycols, using surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS). It was found that the size and interconnection state of the NPF ligament as well as the surface modification are key parameters that affect the laser desorption/ionization performance. Compared with 2,5-dihydroxybenzoic acid, pristine NPF, and aminobenzenethiol or 3-mercaptopropanoic acid modified Au NPFs, cysteine modified Au NPF generated intense and background-suppressing mass spectra. Regarding the effect of Au NPF morphology, the Au NPF with nanopores in the range of 10-30 nm, ligament size of 5 nm, and electrochemistry surface area of 26.1 m(2)/g exhibited the highest performance as a substrate. This high-performance NPFs can be easily fabricated by capping agent replacement induced self-organization of ultrathin nanowires, followed by self-assembling of a monolayer (SAM) of cysteine. The good thermal/electroconductivity and uniformity of Au NPFs avoided the fragmentation of analytes, eliminated the intrinsic matrix ions interference, and provided good reproducibility (RSD ≤ 10%). Additionally, the fabricated NPFs can be easy divided into microarrays (a ~4 × 4 array from a 1 cm × 1 cm NPF). This work provides a simple and cost-effective route for acquiring an Au nanostructure as a SALDI substrate, which offers a new technique for high-speed analysis of low-molecular weight compounds.

Transformation kinetics of silver nanoparticles and silver ions in aquatic environments revealed by double stable isotope labeling

Silver nanoparticles (AgNPs) are rather mutable in water columns, and the oxidation of AgNPs to release Ag+ and reduction of Ag+ to regenerate AgNPs exist simultaneously in certain environments, making it rather difficult to monitor the reaction kinetics. In this study, we synthesized isotopically labeled AgNPs (99.5% 107Ag, 107AgNPs) and AgNO3 (99.81% 109Ag, 109AgNO3). For the first time, two stable Ag isotopes were used in the same experiment to track the transformation kinetics of AgNPs and Ag+ independently in aquatic environments. It was found that the oxidation of AgNPs dominated the reaction in simple water solutions containing both 107AgNPs and 109Ag+. Sunlight significantly accelerated the dissolution of the 107AgNPs, but longer solar irradiation (8 h) triggered aggregation of the 107AgNPs and therefore reduced the reaction rate. With the addition of 5 mg C L−1 dissolved organic matter, the reduction of 109Ag+ played the leading role. The corrected concentration of dissolved 107Ag+ began to decrease after some time, indicating other reduction mechanisms were happening. An elevated pH (pH 8.5) could even completely inhibit the oxidation of 107AgNPs. All the reactions seemed stalled at low temperature (6 °C) except the dissolution of 107AgNPs under solar irradiation, suggesting a non-negligible effect of sunlight. The presence of divalent cations induced agglomeration of 107AgNPs, but the reduction of 109Ag+ was not significantly affected. These findings implied that the transformation between AgNPs and Ag+ was rather complex and greatly depended on the external conditions. Given the fact that Ag+ has been shown to be much more toxic than AgNPs, the speciation change may dramatically impact the final toxicity and bioavailability of AgNPs, so there is a high demand for assessing the environmental risks of AgNPs under more realistic conditions.

Elemental Mass Size Distribution for Characterization, Quantification and Identification of Trace Nanoparticles in Serum and Environmental Waters

Accurate characterization, quantification, and identification of nanoparticles (NPs) are essential to fully understand the environmental processes and effects of NPs. Herein, the elemental mass size distribution (EMSD), which measures particle size, mass, and composition, is proposed for the direct size characterization, mass quantification, and composition identification of trace NPs in complex matrixes. A one-step method for the rapid measurement of EMSDs in 8 min was developed through the online coupling of size-exclusion chromatography (SEC) with inductively coupled plasma mass spectrometry (ICP-MS). The use of a mobile phase with a relatively high ionic strength (a mixture of 2% FL-70 and 2 mM Na2S2O3) ensured the complete elution of different-sized NPs from the column and, therefore, a size-independent response. After application of a correction for instrumental broadening by a method developed in this study, the size distribution of NPs by EMSD determination agreed closely with that obtained from transmission electron microscopy (TEM) analysis. Compared with TEM, EMSD allows a more rapid determination with a higher mass sensitivity (1 pg for gold and silver NPs) and comparable size discrimination (0.27 nm). The proposed EMSD-based method was capable of identifying trace Ag2S NPs and core-shell nanocomposite Au@Ag, as well as quantitatively tracking the dissolution and size transformation of silver nanoparticles in serum and environmental waters.

Speciation Analysis of Labile and Total Silver(I) in Nanosilver Dispersions and Environmental Waters by Hollow Fiber Supported Liquid Membrane Extraction.

Hollow fiber supported liquid membrane (HFSLM) extraction was coupled with ICP-MS for speciation analysis of labile Ag(I) and total Ag(I) in dispersions of silver nanoparticles (AgNPs) and environmental waters. Ag(I) in aqueous samples was extracted into the HFSLM of 5%(m/v) tri-n-octylphosphine oxide in n-undecane, and stripped in the acceptor of 10 mM Na2S2O3 and 1 mM Cu(NO3)2 prepared in 5 mM NaH2PO4-Na2HPO4 buffer (pH 7.5). Negligible depletion and exhaustive extraction were conducted under static and 250 rpm shaking to extract the labile Ag(I) and total Ag(I), respectively. The extraction equilibration was reached in 8 h for both extraction modes. The extraction efficiency and detection limit were (2.97 ± 0.25)% and 0.1 μg/L for labile Ag(I), and (82.3 ± 2.0)% and 0.5 μg/L for total Ag(I) detection, respectively. The proposed method was applied to determine labile Ag(I) and total Ag(I) in different sized AgNP dispersions and real environmental waters, with spiked recoveries of total Ag(I) in the range of 74.0-98.1%. With the capability of distinguishing labile and total Ag(I), our method offers a new approach for evaluating the bioavailability and understanding the fate and toxicity of AgNPs in aquatic systems.

Controlled Assembly of Gold Nanostructures on a Solid Substrate via Imidazole Directed Hydrogen Bonding for High Performance Surface Enhance Raman Scattering Sensing of Hypochlorous Acid.

Here, we report an efficient and facile method for constructing plasmonic gold nanostructures with controlled morphology on a Si wafer and its use as a surface enhanced Raman scattering (SERS) reporting system for specific detection of HClO. To achieve this substrate, the core gold nanoparticles (AuNPs, ∼100 nm) with a monolayer of 4-mercaptoimidazole (MI) ligands were covalently linked to a thiol-derived Si wafer (MI-AuNPs@SH-Si). Taking advantage of the intermolecular NH···N hydrogen bond (HB) provided by the neighboring imidazole moiety, multiple satellite AuNPs (∼12 nm) decorated with both MI and a Raman reporter are assembled around the core MI-AuNPs at pH 5.0. The uniform morphology of the AuNP-based nanostructures on the Si wafer offer a high density of hot spots with good SERS performance for detecting HClO. The fast oxidation of the imidazole moieties by HClO causes HB destruction and therefore separation of the satellite AuNPs from the core AuNPs, which gives rise to SERS signal damping of the chip that is employed for HClO analysis. This simple and cost-effective method is highly selective for HClO over common interferences and several reactive oxygen/nitrogen species, and enabled rapid analysis at concentrations as low as 1.2 μmol L(-1). The present approach is applied to analyze water and human serum samples with satisfactory results.

Separation and Determination of Silver Nanoparticles

The accurate analysis of silver nanoparticles AgNPs in complicated environmental and biological matrix is the premise for the assessment of AgNP risks. In the past few decades, a myriad of methods have been developed for the concentration and determination of AgNPs. In this chapter, methodologies for the separation, characterization, and quantification of AgNPs are introduced, and the advantages and shortcomings of each technique are also discussed. In most cases, multiple schemes are often needed to get comprehensive information of the analytes. To meet the ultra-trace detection of AgNPs in the environment, techniques with higher resolution and sensitivity are required.