Vambola Kisand

Size-Dependent Toxicity of Silver Nanoparticles to Bacteria, Yeast, Algae, Crustaceans and Mammalian Cells In Vitro

The concept of nanotechnologies is based on size-dependent properties of particles in the 1–100 nm range. However, the relation between the particle size and biological effects is still unclear. The aim of the current paper was to generate and analyse a homogenous set of experimental toxicity data on Ag nanoparticles (Ag NPs) of similar coating (citrate) but of 5 different primary sizes (10, 20, 40, 60 and 80 nm) to different types of organisms/cells commonly used in toxicity assays: bacterial, yeast and algal cells, crustaceans and mammalian cells in vitro. When possible, the assays were conducted in ultrapure water to minimise the effect of medium components on silver speciation. The toxic effects of NPs to different organisms varied about two orders of magnitude, being the lowest (∼0.1 mg Ag/L) for crustaceans and algae and the highest (∼26 mg Ag/L) for mammalian cells. To quantify the role of Ag ions in the toxicity of Ag NPs, we normalized the EC50 values to Ag ions that dissolved from the NPs. The analysis showed that the toxicity of 20–80 nm Ag NPs could fully be explained by released Ag ions whereas 10 nm Ag NPs proved more toxic than predicted. Using E. coli Ag-biosensor, we demonstrated that 10 nm Ag NPs were more bioavailable to E. coli than silver salt (AgNO3). Thus, one may infer that 10 nm Ag NPs had more efficient cell-particle contact resulting in higher intracellular bioavailability of silver than in case of bigger NPs. Although the latter conclusion is initially based on one test organism, it may lead to an explanation for “size-dependent“ biological effects of silver NPs. This study, for the first time, investigated the size-dependent toxic effects of a well-characterized library of Ag NPs to several microbial species, protozoans, algae, crustaceans and mammalian cells in vitro.

Toxicity of 11 Metal Oxide Nanoparticles to Three Mammalian Cell Types In Vitro.

The knowledge on potential harmful effects of metallic nanomaterials lags behind their increased use in consumer products and therefore, the safety data on various nanomaterials applicable for risk assessment are urgently needed. In this study, 11 metal oxide nanoparticles (MeOx NPs) prepared using flame pyrolysis method were analyzed for their toxicity against human alveolar epithelial cells A549, human epithelial colorectal cells Caco2 and murine fibroblast cell line Balb/c 3T3. The cell lines were exposed for 24 h to suspensions of 3-100 μg/mL MeOx NPs and cellular viability was evaluated using. Neutral Red Uptake (NRU) assay. In parallel to NPs, toxicity of soluble salts of respective metals was analyzed, to reveal the possible cellular effects of metal ions shedding from the NPs. The potency of MeOx to produce reactive oxygen species was evaluated in the cell-free assay. The used three cell lines showed comparable toxicity responses to NPs and their metal ion counterparts in the current test setting. Six MeOx NPs (Al2O3, Fe3O4, MgO, SiO2, TiO2, WO3) did not show toxic effects below 100 µg/mL. For five MeOx NPs, the averaged 24 h IC50 values for the three mammalian cell lines were 16.4 µg/mL for CuO, 22.4 µg/mL for ZnO, 57.3 µg/mL for Sb2O3, 132.3 µg/mL for Mn3O4 and 129 µg/mL for Co3O4. Comparison of the dissolution level of MeOx and the toxicity of soluble salts allowed to conclude that the toxicity of CuO, ZnO and Sb2O3 NPs was driven by release of metal ions. The toxic effects of Mn3O4 and Co3O4 could be attributed to the ROS-inducing ability of these NPs. All the NPs were internalized by the cells according to light microscopy studies but also proven by TEM, and internalization of Co3O4 NPs seemed to be most prominent in this aspect. In conclusion, this work provides valuable toxicological data for a library of 11 MeOx NPs. Combining the knowledge on toxic or non-toxic nature of nanomaterials may be used for safe-by-design approach.

Photocatalytic antibacterial activity of nano-TiO2 (anatase)-based thin films: Effects on Escherichia coli cells and fatty acids

Titanium dioxide is a photocatalyst with well-known ability to oxidise a wide range of organic contaminants as well as to destroy microbial cells. In the present work TiO2 nanoparticles with high specific surface area (150m(2)/g) were used to prepare nanostructured films. The TiO2 nanoparticle-based film in combination with UV-A illumination with intensity (22W/m(2)) comparable to that of the sunlight in the UV-A region was used to demonstrate light-induced antibacterial effects. Fast and effective inactivation of Escherichia coli cells on the prepared thin films was observed. Visualization of bacterial cells under scanning electron microscopy (SEM) showed enlargement of the cells, distortion of cellular membrane and possible leakage of cytoplasm after 10min of exposure to photoactivated TiO2. According to the plate counts there were no viable cells as early as after 20min of exposure to UV-A activated TiO2. In parallel to effects on bacterial cell viability and morphology, changes in saturated and unsaturated fatty acids - important components of bacterial cell membrane-were studied. Fast decomposition of saturated fatty acids and changes in chemical structure of unsaturated fatty acids were detected. Thus, we suggest that peroxidation and decomposition of membrane fatty acids could be one of the factors contributing to the morphological changes of bacteria observed under SEM, and ultimately, cell death.

Dissolution of silver nanowires and nanospheres dictates their toxicity to Escherichia coli.

Silver nanoparticles are extensively used in antibacterial applications. However, the mechanisms of their antibacterial action are not yet fully explored. We studied the solubility-driven toxicity of 100 × 6100 nm (mean primary diameter × length) silver nanowires (NWs) to recombinant bioluminescent Escherichia coli as a target representative of enteric pathogens. The bacteria were exposed to silver nanostructures in water to exclude the speciation-driven alterations. Spherical silver nanoparticles (83 nm mean primary size) were used as a control for the effect of NPs shape. Toxicity of both Ag NWs and spheres to E. coli was observed at similar nominal concentrations: the 4h EC50 values, calculated on the basis of inhibition of bacterial bioluminescence, were 0.42 ± 0.06 and 0.68 ± 0.01 mg Ag/L, respectively. Dissolution and bioavailability of Ag from NWs and nanospheres, analyzed with AAS or Ag-sensor bacteria, respectively, suggested that the toxic effects were caused by solubilized Ag+ ions. Moreover, the antibacterial activities of Ag NWs suspension and its ultracentrifuged particle-free supernatant were equal. The latter indicated that the toxic effects of ~80–100 nm Ag nanostructures to Escherichia coli were solely dependent on their dissolution and no shape-induced/related effects were observed. Yet, additional nanospecific effects could come into play in case of smaller nanosilver particles.

Photocatalytic activity of non-stoichiometric ZnFe2O4 under visible light irradiation

Nanostructured zinc ferrites with different excess iron contents (ZnFe2+zO4, where z = 0.00, 0.05, 0.10 and 0.15) have been synthesized using the sol–gel auto-combustion method. The effect of excess iron on the structural, optical and visible light photocatalytic activity of zinc ferrite samples has been investigated. X-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), x-ray magnetic circular dichroism (XMCD), Brunauer–Emmett–Teller theory, scanning electron microscopy (SEM), diffuse reflectance spectroscopy (UV–Vis) and photoluminescence spectroscopy were used to characterize the synthesized non-stoichiometric ZnFe2O4 powders. The XRD patterns demonstrated that the samples consist of single phase spinel structure with crystallite sizes of ~25 nm. SEM analysis indicated that the nanosized particles grow together in porous clusters with a size of several microns. The XPS and XMCD analyses revealed that the excess iron ion substitutes Zn2+ in tetrahedral sites and in octahedral sites Fe2+ can be found in addition to Fe3+, which could be created to restore the overall charge balance in the crystal lattice. Stoichiometric zinc ferrite (ZnFe2+zO4, z = 0.00) exhibited higher photocatalytic activity (40%) than the excess iron sample (ZnFe2+zO4, z = 0.15, i.e. 4%) under visible light irradiation for 3 h. This was explained by the formation of Fe2+ in the octahedral sites of excess iron ZnFe2O4; these species act as recombination centres.

LOW TEMPERATURE OPTICAL SPECTROSCOPY OF NONLINEAR BBO CRYSTALS

The absorption reflection and luminescence excitation spectra, as well as the x-ray excited stationary and thermostimulated luminescence spectra of BBO crystals have been measured over a wide spectral (4–30 eV) and temperature (8–300 K) range. The experimental data show that the formation of the absorption edge of the crystal is strongly affected by excitonic-type excitations.

Luminescence of cation excitons in and crystals in a wide excitation VUV region

Host luminescence excitation spectra and reflection spectra of and crystals at low temperatures have been measured in the energy region of 4-30 eV using synchrotron radiation. High-efficiency host luminescence is connected to radiative decay of self-trapped cation excitons. It is shown that also in the region of excitation multiplication, e.g. if the excitation energy is larger than twice the band gap energy , and in the relaxation process of core excitons the radiative self-trapped cation excitons are formed. However, the recombination of hole and self-trapped electrons (band-band excitation) does not give rise to host luminescence.

Pinching of alkoxide jets—a route for preparing nanometre level sharp oxide fibres

The pinching phenomenon is used to shape jets of Sn(OBu)4 based viscous oligomeric melts into nanometre range sharp oxide needles. The influence of viscosity of the liquid, humidity of surrounding environment and pulling speed on formation of the needles is investigated. Optimal conditions enable reproducible preparation of needles that have tip radii down to 15–25 nm, i.e. in the range that is of considerable interest for many nanotechnological applications.

A straightforward and “green” solvothermal synthesis of Al doped zinc oxide plasmonic nanocrystals and piezoresistive elastomer nanocomposite

Plasmonic oxide nanocrystals hold great promise in a wide range of applications, for which the availability of scalable and “green” synthesis methods is prerequisite, whereas until recently an excellent response has been demonstrated only for samples prepared through intricate synthesis paths. We report here a simple ethanol solvothermal synthesis route of Al doped ZnO plasmonic nanocrystals (Zn1−xAlxO) at doping levels of x up to 0.15. The obtained Al doped ZnO samples consisted of nanoparticles and short nanorods with a diameter of around 10 nm at x = 0.15 doping level while reaching aspect ratio levels of 50 for lower doping levels. Detailed structural studies using powder X-ray diffraction Rietveld refinement, X-ray absorption and photoelectron spectroscopies show that all samples maintain the structure of the phase-pure zincite with the space group P63mc. The resulting powders exhibit strong infrared absorption while remaining largely transparent for visible light, enabling the preparation of transparent colloidal dispersions. Furthermore, as a test of applicability in a practical device, the nanocrystals were used to prepare transparent piezoresistive Zn0.925Al0.075O–polydimethylsiloxane composites. The prepared sensor material exhibits excellent repeatable and reproducible piezoresistive behaviour.

TiO2 nanowire dispersions in viscous polymer matrix: electrophoretic alignment and optical properties

The changes in optical properties during TiO₂ nanowire orientation in polydimethylsiloxane (PDMS) matrix under the influence of an electric field are strongly influenced by nanowire (NW) diameter. It was demonstrated for the first time that either positive or negative change in transmittance can be induced by NW alignment parallel to the electric field depending on the NW diameter. These effects can be explained by the interplay between scattering and reflectance. Experimental findings reported could be important for smart window applications for the regulation of visible or even infrared transparency, thus reducing the energy consumption by air conditioning systems in buildings and automobiles in the future.