Early ecotoxic effects of ZnO nanoparticle chronic exposure in Mytilus galloprovincialis revealed by transcription of apoptosis and antioxidant-related genes.

Recently, China became one of the largest nanomaterial markets in the world. The wide use of ZnO nanoparticles in a number of products implies an increasing release in marine environment and consequently the evaluation of the potential effects upon marine organisms largely cultured in China for commercial purposes, such as invertebrate bivalves is a current need. To this aim, survival, bioaccumulation, and transcription pattern of key genes, p53, PDRP, SOD, CAT, and GST, involved in DNA damage/repair and antioxidation, in Mytilus galloprovincialis digestive gland, exposed to ZnO NPs (<100 nm) and ZnO bulk (150-200 nm) for 4 weeks, were evaluated. ZnSO4 was also assessed to appraise the role of zinc ions. Starting from 72 h, increasing mortality values along the exposure time were observed for all ZnO compounds. The highest difference was evident after 28 d when NPs resulted three times more toxic than bulk, (LC50) = 0.78 mg Zn/L (confidence limits: 0.64, 1.00) and 2.62 mg Zn/L (confidence limits: 1.00, 4.00), respectively. For ZnSO4 the (LC50) was always the lowest reaching the minimum value at 28 d 0.25 mg Zn/L (confidence limits: 0.10-0.40). Digestive gland showed higher uptake rate of ionic Zn respect to ZnO NPs and bulk during the first three days of exposure. In particular at the end of the exposure time (28 d) at 1 mg Zn/L the rank of Zn uptake rate was Zinc ion > ZnO NPs > ZnO bulk. The relative expression of investigated genes evidenced that distinct actions of apoptosis and antioxidation occurred in M. galloprovincialis exposed to ZnO NPs with a peculiar pattern dependent on exposure time and concentration. Application of the qRT-PCR technique revealed evidence of sensitivity to the nanomaterial since the first time of exposure.

AC electric field for rapid assembly of nanostructured polyaniline onto microsized gap for sensor devices.

Interconnected network of nanostructured polyaniline (PANI) is giving strong potential for enhancing device performances than bulk PANI counterparts. For nanostructured device processing, the main challenge is to get prototypes on large area by requiring precision, low cost and high rate assembly. Among processes meeting these requests, the alternate current electric fields are often used for nanostructure assembling. For the first time, we show the assembly of nanostructured PANI onto large electrode gaps (30-60 µm width) by applying alternate current electric fields, at low frequencies, to PANI particles dispersed in acetonitrile (ACN). An important advantage is the short assembly time, limited to 5-10 s, although electrode gaps are microsized. That encouraging result is due to a combination of forces, such as dielectrophoresis (DEP), induced-charge electrokinetic (ICEK) flow and alternate current electroosmotic (ACEO) flow, which speed up the assembly process when low frequencies and large electrode gaps are used. The main achievement of the present study is the development of ammonia sensors created by direct assembling of nanostructured PANI onto electrodes. Sensors exhibit high sensitivity to low gas concentrations as well as excellent reversibility at room temperature, even after storage in air.

Green Anisole as Antisolvent in Planar Triple-Cation Perovskite Solar Cells with Varying Cesium Concentrations.

The feasibility of replacing toxic chlorobenzene antisolvents with environmentally friendly anisole in the fabrication of planar triple-cation perovskite solar cells was explored here. The successful integration of anisole not only ensures comparable device performance but also contributes to the development of more sustainable and green fabrication processes for next-generation photovoltaic technologies. Nevertheless, to ensure the possibility of achieving well-functioning unencapsulated devices whose working operation depends on outdoor atmospheric conditions, we found that adjusting the cesium concentrations in the perovskite layers enabled the electrical characterization of efficient devices even under high relative humidity conditions (more than 40%). We found that 10% of CsI in the precursor solution will make devices with low hysteresis indexes and sustained performance stability over a 90-day period both with cholorobenzene and anisole antisolvent. These results further confirm that green anisole can replace chlorobenzene as an antisolvent.

The effect of solvent on the morphology of ZnO nanostructure assembly by dielectrophoresis and its device applications.

Different zinc oxide nanostructured morphologies were grown on photolithographically patterned silicon/silicon dioxide substrates by dielectrophoresis technique using different solvents, such as water and ethanol, obtaining rod-like and net-like nanostructures, respectively. The formation of continuous nanostructures was confirmed by scanning electron microscopic, atomic force microscopic images, and electrical characterizations. The rod-like zinc oxide nanostructures were observed in the 10 µm gap between the fingers in the pattern, whereas net-like nanostructures were formed independently of microgap. A qualitative study about the mechanism for the assembly of zinc oxide continuous nanostructures was presented. Devices were electrically characterized, at room temperature, in controlled environment to measure the conductance behavior in ultraviolet and humidity environment. Devices based on zinc oxide nanostructures grown in ethanol medium show better responses under both ultraviolet and humidity, because of the net-like structure with high surface-to-volume ratio.

Different sizes of ZnO diversely affected the cytogenesis of the sea urchin Paracentrotus lividus.

Today nanoparticles (NPs) have many applications in commercial products due to their small size and peculiar properties that, conversely, make them potentially toxic for humans and the environment. ZnO NPs are largely used in many personal care products, such as sunscreens and cosmetics. In this study the cytotoxic effects of ZnO particles with different sizes (ZnO Bulk, >100nm; ZnO NPs, 100nm and ZnO NPs, 14nm) upon the first developmental stages of the sea urchin Paracentrotus lividus, are evaluated. Morphological alterations are also assessed by embryotoxicity tests. The cytogenetic analysis highlighted that ZnO NPs interfere with cell cycle inducing a dose-dependent decrease of mitotic activity and chromosomal aberrations at higher concentrations (30µM). Moreover, the larval development was affected by ZnO NPs 100nm (EC50=0.46 [0.30-0.63] µM [Zn]) in a dose-dependent way. Size-dependent toxicity was instead not obtained for ZnO NPs. From our results could be highlighted that the presence of embryos, blocked in pre-larval stage, could be due to the induction of chromosome aberrations by ZnO particles, confirming that cytogenetic analyses allow evaluating possible NPs action mechanisms.

Comparative toxicity of nano ZnO and bulk ZnO towards marine algae Tetraselmis suecica and Phaeodactylum tricornutum.

The wide use of ZnO nanoparticles in a number of products implies an increasing release into the marine environment, resulting in the need to evaluate the potential effects upon organisms, and particularly phytoplankton, being at the base of the throphic chain. To this aim, dose-response curves for the green alga Tetraselmis suecica and the diatom Phaeodactylum tricornutum derived from the exposure to nano ZnO (100 nm) were evaluated and compared with those obtained for bulk ZnO (200 nm) and ionic zinc. The toxic effects to both algae species were reported as no observable effect concentration (NOEC) of growth inhibition and as 1, 10, and 50% effect concentrations (EC1, EC10, and EC50). The toxicity decreased in the order nano ZnO > Zn2+ > bulk ZnO. EC50 values for nano ZnO were 3.91 [3.66-4.14] mg Zn/L towards the green microalgae and 1.09 [0.96-1.57] mg Zn/L towards the diatom, indicating a higher sensitivity of P. tricornutum. The observed diverse effects can be ascribed to the interaction occurring between different algae and ZnO particles. Due to algae motility, ZnO particles were intercepted in different phases of aggregation and sedimentation processes, while algae morphology and size can influence the level of entrapment by NP aggregates.This underlines the need to take into account the peculiarity of the biological system in the assessment of NP toxicity.

Toxic effects of ZnO nanoparticles towards marine algae Dunaliella tertiolecta.

Dose response curve and population growth rate alterations of marine Chlorophyte Dunaliella tertiolecta derived from the exposure to ZnO nanoparticles were evaluated. Bulk ZnO and ionic zinc were also investigated for comparison. At the same time, the aggregation state and particle size distribution were monitored. The evaluated 50% effect concentration (EC50 1.94 [0.78-2.31] mg Zn L(-1)) indicates that nano ZnO is more toxic than its bulk counterpart (EC50 3.57 [2.77-4.80] mg Zn L(-1)). Cross-referencing the toxicity parameters calculated for ZnCl(2) (EC50 0.65 [0.36-0.70] mg Zn L(-1)) and the dissolution properties of the ZnO, it can be gathered that the higher toxicity of nano ZnO is most likely related to the peculiar physicochemical properties of the nanostate with respect to the bulk material. Furthermore growth rate of D. tertiolecta was significantly affected by nano ZnO exposure. Our findings suggest that the primary particle size of the dispersed particles affect the overall toxicity.

Embryotoxicity and spermiotoxicity of nanosized ZnO for Mediterranean sea urchin Paracentrotus lividus.

The effect of nano ZnO (nZnO) upon the fertilization and early development of embryos of the Mediterranean sea urchin Paracentrotus lividus is reported herein for the first time. Zn ion (ZnCl2) and bulk ZnO (bZnO) toxicity were assessed for comparison. The embryotoxicity tests showed a 100% effect already at 1 µM of nZnO (expressed as [Zn]) while bZnO and ZnCl2 showed EC50s of 0.98 [0.88-1.19] µM [Zn] and 2.02 [1.97-2.09] µM [Zn], respectively. Noteworthy, the frequency of developmental defects for the three compounds was dissimilar and a specific trend for larval skeletal abnormality produced by nZnO was observed. The sperm fertilization capability was only slightly affected by the tested chemicals while the effects were dramatic on the offspring quality of sperms exposed to ZnO compounds resulting in an early block of the regular larval development. ZnO toxicity seems related not only to Zinc ions but also to some surface interactions of particle/aggregates with target organisms and/or with the seawater.

Investigation of ZnO nanoparticles' ecotoxicological effects towards different soil organisms.

INTRODUCTION: Nanomaterials have widespread applications in several industrial sectors. ZnO nanoparticles (NPs) are among the most commonly used metal oxide NPs in personal care products, coating and paints. However, their potential toxicological impact on the environment is largely unexplored. MATERIALS AND METHODS: The aim of this work was to evaluate whether ZnO nanoparticles exert toxic and genotoxic effects upon terrestrial organisms: plants (Lepidium sativum, Vicia faba), crustaceans (Heterocyipris incongruens), insects (Folsomia candida). To achieve this purpose, organisms pertaining to different trophic levels of the soil ecosystem have been exposed to ZnO NPs. In parallel, the selected soil organisms have been exposed to the same amount of Zn in its ionic form (Zn(2+)) and the effects have been compared. RESULTS: The most conspicuous effect, among the test battery organisms, was obtained with the ostracod H. incongruens, which was observed to be the most sensitive organism to ZnO NPs. The root elongation of L. sativum was also mainly affected by exposure to ZnO NPs with respect to ZnCl(2), while collembolan reproduction test produced similar results for both Zn compounds. Slight genotoxic effects with V. faba micronucleus test were observed with both soils. CONCLUSION: Nanostructured ZnO seems to exert a higher toxic effect in insoluble form towards different terrestrial organisms with respect to similar amounts of zinc in ionic form.