Chromium and cobalt in leather: A Danish market survey.

INTRODUCTION: Leather has been a significant source of chromium (Cr) allergy in Denmark since the 1990s. More recently, cobalt (Co) allergy has been identified in leather as a source of allergic contact dermatitis. OBJECTIVES: To measure Cr and Co levels in Danish leather goods. METHODS: A total of 87 leather samples were collected, all tanned in Europe. Handheld X-ray fluorescence (XRF) device was used to screen for the presence of Cr and Co. The 20 leather samples with the highest concentrations of Co and Co were tested using International Organization for Standardization (ISO)-standards. RESULTS: XRF analysis showed Cr in 78/87 (83.9%) samples and Co in 52/87 (59.7%), with average concentrations of 41 mg/kg (range: 0.0-77 mg/kg) and 0.22 mg/kg (range: 0.0-2.9 mg/kg), respectively. ISO 10195 and 17 075-1 testing identified Cr (VI) in 7 out of 20 samples (1.4; 0.3-4.2 mg/kg), while ISO 17072-1 detected Co in 6 of 20 samples, averaging 3.95 mg/kg (range: 0.22-7.9 mg/kg). CONCLUSION: Most leather samples contained Cr, which was expected, while Cr (VI) was detectable in seven out of twenty tested samples but only detected in one product above the regulatory limit of 3 mg/kg. A potentially significant concentration was found for Co.

Adsorption of Horseradish Peroxidase on Metallic Nanoparticles: Effects on Reactive Oxygen Species Detection Using 2',7'-Dichlorofluorescin Diacetate.

The fluorescent probe 2',7'-dichlorofluorescein diacetate (DCFH-DA) together with the enzyme horseradish peroxidase (HRP) is widely used in nanotoxicology to study acellular reactive oxygen species (ROS) production from nanoparticles (NPs). This study examined whether HRP adsorbs onto NPs of Mn, Ni, and Cu and if this surface process influences the extent of metal release and hence the ROS production measurements using the DCFH assay in phosphate buffered saline (PBS), saline, or Dulbecco's modified Eagle's medium (DMEM). Adsorption of HRP was evident onto all NPs and conditions, except for Mn NPs in PBS. The presence of HRP resulted in an increased release of copper from the Cu NPs in PBS and reduced levels of nickel from the Ni NPs in saline. Both metal ions in solution and the adsorption of HRP onto the NPs can change the activity of HRP and thus influence the ROS results. The effect of HRP on the NP reactivity was shown to be solution chemistry dependent. Most notable was the evident affinity/adsorption of phosphate toward the metal NPs, followed by a reduced adsorption of HRP, the concomitant reduction in released manganese from the Mn NPs, and increased levels of released metals from the Cu NPs in PBS. Minor effects were observed for the Ni NPs. The solution pH should be monitored since the release of metals can change the solution pH and the activity of HRP is known to be pH-dependent. It is furthermore essential that solution pH adjustments are made following the addition of NaOH during diacetyl removal of DCFH-DA. Even though not observed for the given exposure conditions of this study, released metal ions could possibly induce agglomeration or partial denaturation of HRP, which in turn could result in steric hindrance for H2O2 to reach the active site of HRP. This study further emphasizes the influence of HRP on the background kinetics, its solution dependence, and effects on measured ROS signals. Different ways of correcting for the background are highlighted, as this can result in different interpretations of generated results. The results show that adsorption of HRP onto the metal NPs influenced the extent of metal release and may, depending on the investigated system, result in either under- or overestimated ROS signals if used together with the DCFH assay. HRP should hence be used with caution when measuring ROS in the presence of reactive metallic NPs.

Cobalt nanoparticles trigger ferroptosis-like cell death (oxytosis) in neuronal cells: Potential implications for neurodegenerative disease.

The neurotoxicity of hard metal-based nanoparticles (NPs) remains poorly understood. Here, we deployed the human neuroblastoma cell line SH-SY5Y differentiated or not into dopaminergic- and cholinergic-like neurons to study the impact of tungsten carbide (WC) NPs, WC NPs sintered with cobalt (Co), or Co NPs versus soluble CoCl2 . Co NPs and Co salt triggered a dose-dependent cytotoxicity with an increase in cytosolic calcium, lipid peroxidation, and depletion of glutathione (GSH). Co NPs and Co salt also suppressed glutathione peroxidase 4 (GPX4) mRNA and protein expression. Co-exposed cells were rescued by N-acetylcysteine (NAC), a precursor of GSH, and partially by liproxstatin-1, an inhibitor of lipid peroxidation. Furthermore, in silico analyses predicted a significant correlation, based on similarities in gene expression profiles, between Co-containing NPs and Parkinson's disease, and changes in the expression of selected genes were validated by RT-PCR. Finally, experiments using primary human dopaminergic neurons demonstrated cytotoxicity and GSH depletion in response to Co NPs and CoCl2 with loss of axonal integrity. Overall, these data point to a marked neurotoxic potential of Co-based but not WC NPs and show that neuronal cell death may occur through a ferroptosis-like mechanism.

In the Search for Nanospecific Effects of Dissolution of Metallic Nanoparticles at Freshwater-Like Conditions: A Critical Review.

Knowledge on relations between particle properties and dissolution/transformation characteristics of metal and metal oxide nanoparticles (NPs) in freshwater is important for risk assessment and product development. This critical review aims to elucidate nanospecific effects on dissolution of metallic NPs in freshwater and similar media. Dissolution rate constants are compiled and analyzed for NPs of silver (Ag), copper (Cu), copper oxide/hydroxide (CuO, Cu(OH)2), zinc oxide (ZnO), manganese (Mn), and aluminum (Al), showing largely varying (orders of magnitude) constants when modeled using first order kinetics. An effect of small primary sizes (<15 nm) was observed, leading to increased dissolution rate constants and solubility in some cases. However, the often extensive particle agglomeration can result in reduced nanospecific effects on dissolution and also an increased uncertainty related to the surface area, a parameter that largely influence the extent of dissolution. Promising ways to model surface areas of NPs in solution using fractal dimensions and size distributions are discussed in addition to nanospecific aspects related to other processes such as corrosion, adsorption of natural organic matter (NOM), presence of capping agents, and existence of surface defects. The importance of the experimental design on the results of dissolution experiments of metal and metal oxide NPs is moreover highlighted, including the influence of ionic metal solubility and choice of particle dispersion methodology.

Optimization of an air-liquid interface exposure system for assessing toxicity of airborne nanoparticles.

The use of refined toxicological methods is currently needed for characterizing the risks of airborne nanoparticles (NPs) to human health. To mimic pulmonary exposure, we have developed an air-liquid interface (ALI) exposure system for direct deposition of airborne NPs on to lung cell cultures. Compared to traditional submerged systems, this allows more realistic exposure conditions for characterizing toxicological effects induced by airborne NPs. The purpose of this study was to investigate how the deposition of silver NPs (AgNPs) is affected by different conditions of the ALI system. Additionally, the viability and metabolic activity of A549 cells was studied following AgNP exposure. Particle deposition increased markedly with increasing aerosol flow rate and electrostatic field strength. The highest amount of deposited particles (2.2 µg cm(-2) ) at cell-free conditions following 2 h exposure was observed for the highest flow rate (390 ml min(-1) ) and the strongest electrostatic field (±2 kV). This was estimated corresponding to deposition efficiency of 94%. Cell viability was not affected after 2 h exposure to clean air in the ALI system. Cells exposed to AgNPs (0.45 and 0.74 µg cm(-2) ) showed significantly (P < 0.05) reduced metabolic activities (64 and 46%, respectively). Our study shows that the ALI exposure system can be used for generating conditions that were more realistic for in vitro exposures, which enables improved mechanistic and toxicological studies of NPs in contact with human lung cells.Copyright © 2016 The Authors Journal of Applied Toxicology Published by John Wiley & Sons Ltd.

Vibrational Sum Frequency Spectroscopy on Polyelectrolyte Multilayers: Effect of Molecular Surface Structure on Macroscopic Wetting Properties.

Adsorption of a single layer of molecules on a surface, or even a reorientation of already present molecules, can significantly affect the surface properties of a material. In this study, vibrational sum frequency spectroscopy (VSFS) has been used to study the change in molecular structure at the solid-air interface following thermal curing of polyelectrolyte multilayers of poly(allylamine hydrochloride) and poly(acrylic acid). Significant changes in the VSF spectra were observed after curing. These changes were accompanied by a distinct increase in the static water contact angle, showing how the properties of the layer-by-layer molecular structure are controlled not just by the polyelectrolyte in the outermost layer but ultimately by the orientation of the chemical constituents in the outermost layers.

Sorption and dissolution of bare and coated silver nanoparticles in soil suspensions--Influence of soil and particle characteristics.

The increasing use of silver nanoparticles (AgNPs) in consumer products triggers the need for investigations that improve the understanding of their chemical transformations upon environmental entry. Such knowledge provides crucial information for toxicological studies and risk assessments. Interactions with the soil compartment need to be explored as there are evident risks of the dispersion of both AgNPs and of released Ag ions/complexes present in wastewater-treated sludge that is distributed onto agricultural land. The dissolution and fractionation in solution of bare (AgNP-bare, noncoated) and coated AgNPs (AgNP-coat, stabilized with two nonionic surfactants, polyoxyethylene glycerol trioleate and Tween 20) were investigated after 4 and 48 h in suspensions of one sandy and one clayey soil of different pHs (3.3, 5.2). Parallel experiments were performed with soil suspensions spiked with easily soluble AgNO3. Silver in the water phase was separated in a dissolved fraction (mainly Ag ions/complexes) and a particle fraction (mainly AgNP/agglomerates/Ag adsorbed on organic matter) by means of ultracentrifugation. Bare AgNPs were nonstable and dissolved to a significantly larger extent in the sandy soil mixture compared to coated AgNPs. The concentration of dissolved Ag (ions/complexes) in the water phase was similar in the case of bare AgNPs and AgNO3 (at pH 3 and 5.2) after 24 h in sandy soil, which implies a high degree of dissolution of bare AgNPs (50-100%). In contrast, approximately 50% of the coated AgNPs remained in the water phase after 48 h of equilibration in the sandy soil at pH 5.2. The clayey soil had a significantly higher sorption capacity of Ag compared with the sandy soil, as Ag in the case of coated AgNPs was only detected in the water phase of pH 5.2 (<1% of added Ag). Ultracentrifugation was proven more efficient compared with microfiltration to separate the dissolved Ag fraction (ions/complexes) and the particle fraction (AgNPs/agglomerates) of the water phase. This fractionation is not a measure of any potential toxicity.

Critical review: Copper runoff from outdoor copper surfaces at atmospheric conditions.

This review on copper runoff dispersed from unsheltered naturally patinated copper used for roofing and facades summarizes and discusses influencing factors, available literature, and predictive models, and the importance of fate and speciation for environmental risk assessment. Copper runoff from outdoor surfaces is predominantly governed by electrochemical and chemical reactions and is highly dependent on given exposure conditions (size, inclination, geometry, degree of sheltering, and orientation), surface parameters (age, patina composition, and thickness), and site-specific environmental conditions (gaseous pollutants, chlorides, rainfall characteristics (amount, intensity, pH), wind direction, temperature, time of wetness, season). The corrosion rate cannot be used to assess the runoff rate. The extent of released copper varies largely between different rain events and is related to dry and wet periods, dry deposition prior to the rain event and prevailing rain and patina characteristics. Interpretation and use of copper runoff data for environmental risk assessment and management need therefore to consider site-specific factors and focus on average data of long-term studies (several years). Risk assessments require furthermore that changes in copper speciation, bioavailability aspects, and potential irreversible retention on solid surfaces are considered, factors that determine the environmental fate of copper runoff from outdoor surfaces.

Sequential studies of silver released from silver nanoparticles in aqueous media simulating sweat, laundry detergent solutions and surface water.

From an increased use of silver nanoparticles (Ag NPs) as an antibacterial in consumer products follows a need to assess the environmental interaction and fate of their possible dispersion and release of silver. This study aims to elucidate an exposure scenario of the Ag NPs potentially released from, for example, impregnated clothing by assessing the release of silver and changes in particle properties in sequential contact with synthetic sweat, laundry detergent solutions, and freshwater, simulating a possible transport path through different aquatic media. The release of ionic silver is addressed from a water chemical perspective, compared with important particle and surface characteristics. Released amounts of silver in the sequential exposures were significantly lower, approximately a factor of 2, than the sum of each separate exposure. Particle characteristics such as speciation (both of Ag ionic species and at the Ag NP surface) influenced the release of soluble silver species present on the surface, thereby increasing the total silver release in the separate exposures compared with sequential immersions. The particle stability had no drastic impact on the silver release as most of the Ag NPs were unstable in solution. The silver release was also influenced by a lower pH (increased release of silver), and cotransported zeolites (reduced silver in solution).

Transport and fate of silver as polymer-stabilised nanoparticles and ions in a pilot wastewater treatment plant, followed by sludge digestion and disposal of sludge/soil mixtures: A case study.

A case study of transport and changes in properties of polymer-stabilised Ag NPs is presented in this paper investigating their interaction in different treatment steps within a fully realistic pilot wastewater treatment plant (WWTP), in anaerobic digested sludge, and in soil/sludge mixtures. The fate of the same Ag NPs was tracked in these environments, hence taking the history of the Ag NPs into account. The results show that most of the Ag NPs end up in the sludge (80-100%), also after anaerobically digestion. Furthermore, the fraction of silver in the supernatant was very low after 48 h incubation with silver-containing digested sludge mixed with different soil types. However, when Ag NPs were added directly to the sludge/soil mixture, soluble silver was present in the supernatant with sandy soil, but not with clayey soil. In all, generated findings show that risk assessments and toxicological studies of Ag NPs suspensions must take into account possible chemical and particle transformations upon environmental entry, as silver in general become less soluble when transported to WWTPs and interacting with sludge, and soil.

Intracellular uptake and toxicity of Ag and CuO nanoparticles: a comparison between nanoparticles and their corresponding metal ions.

UNLABELLED: An increased understanding of nanoparticle toxicity and its impact on human health is essential to enable a safe use of nanoparticles in our society. The aim of this study is to investigate the role of a Trojan horse type mechanism for the toxicity of Ag-nano and CuO-nano particles and their corresponding metal ionic species (using CuCl2 and AgNO3 ), i.e., the importance of the solid particle to mediate cellular uptake and subsequent release of toxic species inside the cell. The human lung cell lines A549 and BEAS-2B are used and cell death/membrane integrity and DNA damage are investigated by means of trypan blue staining and the comet assay, respectively. Chemical analysis of the cellular dose of copper and silver is performed using atomic absorption spectroscopy. Furthermore, transmission electron microscopy, laser scanning confocal microscopy, and confocal Raman microscopy are employed to study cellular uptake and particle-cell interactions. The results confirm a high uptake of CuO-nano and Ag-nano compared to no, or low, uptake of the soluble salts. CuO-nano induces both cell death and DNA damage whereas CuCl2 induces no toxicity. The opposite is observed for silver, where Ag-nano does not cause any toxicity, whereas AgNO3 induces a high level of cell death. IN CONCLUSION: CuO-nano toxicity is predominantly mediated by intracellular uptake and subsequent release of copper ions, whereas no toxicity is observed for Ag-nano due to low release of silver ions within short time periods.

Effect of laundry surfactants on surface charge and colloidal stability of silver nanoparticles.

The stability of silver nanoparticles (Ag NPs) potentially released from clothing during a laundry cycle and their interactions with laundry-relevant surfactants [anionic (LAS), cationic (DTAC), and nonionic (Berol)] have been investigated. Surface interactions between Ag NPs and surfactants influence their speciation and stability. In the absence of surfactants as well as in the presence of LAS, the negatively charged Ag NPs were stable in solution for more than 1 day. At low DTAC concentrations (≤1 mM), DTAC-Ag NP interactions resulted in charge neutralization and formation of agglomerates. The surface charge of the particles became positive at higher concentrations due to a bilayer type formation of DTAC that prevents from agglomeration due to repulsive electrostatic forces between the positively charged colloids. The adsorption of Berol was enhanced when above its critical micelle concentration (cmc). This resulted in a surface charge close to zero and subsequent agglomeration. Extended DLVO theory calculations were in compliance with observed findings. The stability of the Ag NPs was shown to depend on the charge and concentration of the adsorbed surfactants. Such knowledge is important as it may influence the subsequent transport of Ag NPs through different chemical transients and thus their potential bioavailability and toxicity.

Reactive Oxygen Species Formed by Metal and Metal Oxide Nanoparticles in Physiological Media-A Review of Reactions of Importance to Nanotoxicity and Proposal for Categorization.

Diffusely dispersed metal and metal oxide nanoparticles (NPs) can adversely affect living organisms through various mechanisms and exposure routes. One mechanism behind their toxic potency is their ability to generate reactive oxygen species (ROS) directly or indirectly to an extent that depends on the dose, metal speciation, and exposure route. This review provides an overview of the mechanisms of ROS formation associated with metal and metal oxide NPs and proposes a possible way forward for their future categorization. Metal and metal oxide NPs can form ROS via processes related to corrosion, photochemistry, and surface defects, as well as via Fenton, Fenton-like, and Haber-Weiss reactions. Regular ligands such as biomolecules can interact with metallic NP surfaces and influence their properties and thus their capabilities of generating ROS by changing characteristics such as surface charge, surface composition, dissolution behavior, and colloidal stability. Interactions between metallic NPs and cells and their organelles can indirectly induce ROS formation via different biological responses. H2O2 can also be generated by a cell due to inflammation, induced by interactions with metallic NPs or released metal species that can initiate Fenton(-like) and Haber-Weiss reactions forming various radicals. This review discusses these different pathways and, in addition, nano-specific aspects such as shifts in the band gaps of metal oxides and how these shifts at biologically relevant energies (similar to activation energies of biological reactions) can be linked to ROS production and indicate which radical species forms. The influences of kinetic aspects, interactions with biomolecules, solution chemistry (e.g., Cl- and pH), and NP characteristics (e.g., size and surface defects) on ROS mechanisms and formation are discussed. Categorization via four tiers is suggested as a way forward to group metal and metal oxide NPs based on the ROS reaction pathways that they may undergo, an approach that does not include kinetics or environmental variations. The criteria for the four tiers are based on the ability of the metallic NPs to induce Fenton(-like) and Haber-Weiss reactions, corrode, and interact with biomolecules and their surface catalytic properties. The importance of considering kinetic data to improve the proposed categorization is highlighted.

Influence of natural organic matter on the transformation of metal and metal oxide nanoparticles and their ecotoxic potency in vitro.

Increased use and production of engineered nanoparticles (NPs) lead to an elevated risk of their diffuse dispersion into the aquatic environment and increased concern on unknown effects induced by their release into the aquatic ecosystem. An improved understanding of the environmental transformation processes of NPs of various surface characteristics is hence imperative for risk assessment and management. This study presents results on effects of natural organic matter (NOM) on the environmental transformation and dissolution of metal and metal oxide NPs of different surface and solubility properties in synthetic freshwater (FW) with and without NOM. Adsorption of NOM was evident on most of the studied NPs, except Sb and Sb2O3, which resulted in the formation of negatively charged colloids of higher stability and smaller size distribution compared with the same NPs in FW only. The dissolution rate of the NPs in the presence of NOM correlated with the strength of interactions between the carboxylate group of NOM and the particle surface, and resulted in either no (Mn, Sb, ZnO NPs), increased (Co, Sn NPs) and decreased (Ni, NiO, Sb2O3, Y2O3 NPs) levels of dissolution. One type of metal NP from each group (Mn, Ni, Sn) were investigated to assess whether observed differences in adsorption of NOM and dissolution would influence their ecotoxic potency. The results showed Mn, Ni, and Sn NPs to generate intracellular reactive oxygen species (ROS) in a time and dose-dependent manner. The extent of ROS generation in FW was similar for both Mn and Ni NPs but higher for Sn NPs. These findings are possibly related to interactions and infiltration of the NPs with the cells, which lead to redox imbalances which could induce oxidative stress and cell damage. At the same time, the presence of NOM generally reduced the intracellular ROS generation by 20-40% for the investigated NPs and also reduced cytotoxicity of Sn NPs, which can be attributed to the stronger interaction of carboxylate groups of NOM with the surface of the NPs.

Crown ethers at the aqueous solution-air interface: 1. Assignments and surface spectroscopy.

The surface of aqueous solutions of 4-Nitro Benzo-15-Crown-5 (NB15C5) and Benzo-15-Crown-5 (B15C5) has been studied using the surface sensitive technique vibrational sum frequency spectroscopy (VSFS). The NO, CN, COC and CH vibrational modes of these compounds at the air-water interface as well as OH vibrational modes of the surface water hydrating this compound have been targeted in order to obtain molecular information about arrangement and conformation of the adsorbed crown ether molecules at the air-water interface. The CH(2) vibrational modes of crown ethers have been identified and found to be split due to interaction with ether oxygen. The spectra provide evidence for the existence of a protonated crown complex moiety at the surface leading to the appearance of strongly ordered water species. The interfacial water species are influenced by the resulting charged interface and by the strong Zundel polarizability due to tunneling of the proton species between equivalent sites within the crown ring.

Complexation- and ligand-induced metal release from 316L particles: importance of particle size and crystallographic structure.

Iron, chromium, nickel, and manganese released from gas-atomized AISI 316L stainless steel powders (sized <45 and <4 µm) were investigated in artificial lysosomal fluid (ALF, pH 4.5) and in solutions of its individual inorganic and organic components to determine its most aggressive component, elucidate synergistic effects, and assess release mechanisms, in dependence of surface changes using atomic absorption spectroscopy, Raman, XPS, and voltammetry. Complexation is the main reason for metal release from 316L particles immersed in ALF. Iron was mainly released, while manganese was preferentially released as a consequence of the reduction of manganese oxide on the surface. These processes resulted in highly complexing media in a partial oxidation of trivalent chromium to hexavalent chromium on the surface. The extent of metal release was partially controlled by surface properties (e.g., availability of elements on the surface and structure of the outermost surface) and partially by the complexation capacity of the different metals with the complexing agents of the different media. In general, compared to the coarse powder (<45 µm), the fine (<4 µm) powder displayed significantly higher released amounts of metals per surface area, increased with increased solution complexation capacity, while less amounts of metals were released into non-complexing solutions. Due to the ferritic structure of lower solubility for nickel of the fine powder, more nickel was released into all solutions compared with the coarser powder.

Transformation of silver nanoparticles released from skin cream and mouth spray in artificial sweat and saliva solutions: particle size, dissolution, and surface area.

The use of silver nanoparticles (Ag NPs) in consumer products can result in diffuse environmental dispersion of both NPs and ionic silver. This study investigated the transformation of Ag NPs present in two consumer products (skin cream, mouth spray) in terms of release of Ag NPs and ionic silver and changes in particle size in artificial sweat and saliva solutions. Large differences in silver release were observed with the smaller sized Ag NPs in mouth spray releasing more silver compared with the Ag NPs of the skin cream. Substantial particle agglomeration took place in both artificial sweat and saliva, forming large-sized agglomerates (> 100 nm). The amount of dissolved silver in solution after 24 h was less than 10% of the total amount of Ag NPs for both products. The results show that the Ag NPs of these consumer products will largely remain as NPs even after 24 h of skin or saliva contact. The use of normalization by geometric surface area of the particles was tested as a way to compare dissolution for Ag NPs of different characteristics, including pristine, bare, as well as PVP-capped Ag NPs. Normalization of silver dissolution with the geometric surface area was shown promising, but more extensive studies are required to unambiguously conclude whether it is a way forward to enable grouping of the dissolution behavior of Ag NPs released from consumer products.

Adsorption of bio-organic eco-corona molecules reduces the toxic response to metallic nanoparticles in Daphnia magna.

As the use of engineered nanomaterials increases, so does the risk of them spreading to natural ecosystems. Hitherto, knowledge regarding the toxic properties of nanoparticles (NP's) and their potential interactions with natural bio-organic molecules adsorbed to them, and thereby forming surface coronas, is limited. However, we show here that the toxic effect of NPs of tungsten carbide cobalt (WC-Co) and cobalt (Co) on the crustacean Daphnia magna is postponed in the presence of natural biological degradation products (eco-corona biomolecules). For Daphnia exposed to WC-Co NPs the survival time increased with 20-25% and for Co NPs with 30-47% after mixing the particles with a solution of eco-corona biomolecules before exposure. This suggests that an eco-corona, composed of biomolecules always present in natural ecosystems, reduces the toxic potency of both studied NPs. Further, the eco-coronas did not affect the particle uptake, suggesting that the reduction in toxicity was related to the particle-organism interaction after eco-corona formation. In a broader context, this implies that although the increasing use and production of NPs may constitute a novel, global environmental threat, the acute toxicity and long-term effects of some NPs will, at least under certain conditions, be reduced as they enter natural ecosystems.

Detection of gold cysteine thiolate complexes on gold nanoparticles with time-of-flight secondary ion mass spectrometry.

Gold (Au) nanoparticles (NPs) are widely used in nanomedical applications as a carrier for molecules designed for different functionalities. Previous findings suggested that biological molecules, including amino acids, could contribute to the dissolution of Au NPs in physiological environments and that this phenomenon was size-dependent. We, therefore, investigated the interactions of L-cysteine with 5-nm Au NPs by means of time-of-flight secondary ion mass spectrometry (ToF-SIMS). This was achieved by loading Au NPs on a clean aluminum (Al) foil and immersing it in an aqueous solution containing L-cysteine. Upon rinsing off the excessive cysteine molecules, ToF-SIMS confirmed the formation of gold cysteine thiolate via the detection of not only the Au-S bond but also the hydrogenated gold cysteine thiolate molecular ion. The presence of NaCl or a 2-(N-morpholino)ethanesulfonic acid buffer disabled the detection of Au NPs on the Al foil. The detection of larger (50-nm) Au NPs was possible but resulted in weaker cysteine and gold signals, and no detected gold cysteine thiolate signals. Nano-gold specific adsorption of L-cysteine was also demonstrated by cyclic voltammetry using paraffine-impregnated graphite electrodes with deposited Au NPs. We demonstrate that the superior chemical selectivity and surface sensitivity of ToF-SIMS, via detection of elemental and molecular species, provide a unique ability to identify the adsorption of cysteine and formation of gold-cysteine bonds on Au NPs.

Corrosion and transformation of solution combustion synthesized Co, Ni and CoNi nanoparticles in synthetic freshwater with and without natural organic matter.

Pure metallic Co, Ni, and their bimetallic compositions of Co3Ni, CoNi, and CoNi3 nanomaterials were prepared by solution combustion synthesis. Microstructure, phase composition, and crystalline structure of these nanoparticles (NPs) were characterized along with studies of their corrosion and dissolution properties in synthetic freshwater with and without natural organic matter (NOM). The nanomaterials consisted of aggregates of fine NPs (3-30 nm) of almost pure metallic and bimetallic crystal phases with a thin surface oxide covered by a thin carbon shell. The nanomaterials were characterized by BET surface areas ranging from ~ 1 to 8 m2/g for the Ni and Co NPs, to 22.93 m2/g, 14.86 m2/g, and 10.53 m2/g for the Co3Ni, CoNi, CoNi3 NPs, respectively. More Co and Ni were released from the bimetallic NPs compared with the pure metals although their corrosion current densities were lower. In contrast to findings for the pure metal NPs, the presence of NOM increased the release of Co and Ni from the bimetallic NPs in freshwater compared to freshwater only even though its presence reduced the corrosion rate (current density). It was shown that the properties of the bimetallic nanomaterials were influenced by multiple factors such as their composition, including carbon shell, type of surface oxides, and the entropy of mixing.