No abstract

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.

Metallic implants placed in humans exhibit wear and corrosion that result in the liberation of metal-containing by-products. In the case of titanium (Ti) containing implants, the metal containing debris may exist in a number of states, including metallic particles produced by mechanical wear and the products of metal corrosion in biological environments, such as the joints and surrounding fluids and tissues. In addition, these constituents may dissolve in both intracellular and extracellular solutions generating Ti ions. Both species, ions and nanoparticles, show different cellular toxicities. In this work we have evaluated the possible evolution of TiO2 nanoparticles (NPs) into soluble Ti metal ions by contact with biological fluids. For this aim, an in vitro study to address quantitative Ti solubilisation from TiO2 nanoparticles (with a diameter of 21 nm) after incubation with human serum at different concentrations has been conducted. Total Ti determination revealed low solubilisation rates ranging from 0.53 to 0.82% after just one week of incubation in the serum. The incubated serum was then subjected to speciation analysis by anion exchange liquid chromatography using an inductively coupled plasma mass spectrometer (ICP-MS) as an elemental detector for Ti monitoring. The obtained results revealed a significant increase in the Ti signal associated with the fraction of the protein transferrin and preferentially with one of the metal binding sites of the protein, the N-lobe. Thus, the effect of Ti at the cellular level has been evaluated by considering that it can be present either as ions or as nanoparticles using two different cells lines: human enterocytes HT29 and murine osteoblasts MC3T3. Significant toxicity was found at the highest concentration assayed (50 μg mL(-1)) for both Ti species (ions and NPs) and slightly higher for the ionic species at lower concentrations (1 and 10 μg mL(-1)).

This work aims to address simultaneously the presence of gold nanoparticles and gold ionic species in biological samples by HPLC-ICP-MS.

The coupling of SdFFF to ICP-MS/MS might be a prospective tool for the analysis of TiO2 NPs in environmental samples.