Alginate coating modifies the biological effects of cerium oxide nanoparticles to the freshwater bivalve Dreissena polymorpha.

The adsorption of biomacromolecules is a fundamental process that can alter the behaviour and adverse effects of nanoparticles (NPs) in natural systems. While the interaction of NPs with natural molecules present in the environment has been described, their biological impacts are largely unknown. Therefore, this study aims to provide a first evidence of the influence of biomolecules sorption on the toxicity of cerium oxide nanoparticles (CeO2NPs) towards the freshwater bivalve Dreissena polymorpha. To this aim, we compared naked CeO2NPs and coated with alginate and chitosan, two polysaccharides abundant in aquatic environments. Mussels were exposed to the three CeO2NPs (naked, chitosan- and alginate-coated) up to 14 days at 100 µg L-1, which is a concentration higher than the environmental one predicted for this type of NP. A suite of biomarkers related to oxidative stress and energy metabolism was applied, and metabolomics was also carried out to identify metabolic pathways potentially targeted by CeO2NPs. Results showed that the coating with chitosan reduced NP aggregation and increased the stability in water. Nonetheless, the Ce accumulation in mussels was similar in all treatments. As for biological effects, all three types of CeO2NPs reduced significantly the level of reactive oxygen species and the activity of superoxide dismutase, glutathione peroxidase and glutathione-S-transferase. The effect was more pronounced in individuals exposed to CeO2NPs coated with alginate, which also significantly induced the activity of the electron transport system. Metabolomics analysis of amino acid metabolism showed modulation only in mussels treated with CeO2NPs coated with alginate. In this group, 25 metabolites belonging to nucleotides, lipids/sterols and organic osmolytes were also modulated, suggesting that the nanoparticles affect energetic metabolism and osmoregulation of mussels. This study highlights the key role of the interaction between nanoparticles and natural molecules as a driver of nanoparticle ecotoxicity.

Coating with polysaccharides influences the surface charge of cerium oxide nanoparticles and their effects to Mytilus galloprovincialis.

This study focused on the effects of surface coating, acquired through the interaction with natural biomolecules, on the behavior and ecotoxicity of nanoparticles (NPs). To this aim, the effects of Cerium Oxide Nanoparticles (CeO2NPs) naked and coated with chitosan and alginate on the marine mussel Mytilus galloprovincialis were compared. Mussels were exposed for 7 days to 100 µg L-1 of CeO2NPs and for 28 days to 1 µg L-1 of CeO2NPs. In both experiments CeO2NPs were used naked and coated with the two polysaccharides. The lowest tested concentration allowed to understand the environmental relevance of this biological process. A set of biomarkers related to oxidative stress/damage and energy metabolism was applied to assess the ecotoxicity of CeO2NPs. The aggregation and stability in water of CeO2NPs were measured through dynamic light scattering analysis and the levels of Ce in the exposure media and in mussels soft tissues were determined by inductively coupled plasma-mass spectrometry. Results showed a different hydrodynamic behavior and stability of CeO2NPs in saltwater related to the different coatings. Despite this, no differences in the bioaccumulation of CeO2NPs were observed among the experimental groups. Different coatings affected also CeO2NPs toxicological outcomes in both 7- and 28-days exposures. Coating with chitosan enhanced antioxidant enzyme activities while coating with alginate triggered oxidative damage. Although the oxidant pathways did not differ that much among the exposures, biomarkers of energetic supplies suggested a different strategy of defense in response to CeO2NP exposure at a lower concentration and for a longer period of time. The obtained results are in line with findings of a previous study on freshwater mussels, suggesting that the coating with biomolecules, which impart negative charge to the NPs, might enhance their biological effects. This study highlighted that interactions of NPs with natural biomolecules largely present in the aquatic environment could affect NPs toxicity altering the interaction towards organisms.

An Approach for Magnetic Halloysite Nanocomposite with Selective Loading of Superparamagnetic Magnetite Nanoparticles in the Lumen.

We present for the first time a method for the preparation of magnetic halloysite nanotubes (HNT) by loading of preformed superparamagnetic magnetite nanoparticles (SPION) of diameter size ∼6 nm with a hydrodynamic diameter of ∼10 nm into HNT. We found that the most effective route to reach this goal relies on the modification of the inner lumen of HNT by tetradecylphosphonic acid (TDP) to give HNT-TDP, followed by the loading with preformed oleic acid (OA)-stabilized SPION. Transmission electron microscopy evidenced the presence of highly crystalline magnetic nanoparticles only in the lumen, partially ordered in chainlike structures. Conversely, attempts to obtain the same result by exploiting either the positive charge of the HNT inner lumen employing SPIONs covered with negatively charged capping agents or the in situ synthesis of SPION by thermal decomposition were not effective. HNT-TDP were characterized by infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), and ζ-potential, and all of the techniques confirmed the presence of TDP onto the HNT. Moreover, the inner localization of TDP was ascertained by the use of Nile Red, a molecule whose luminescence is very sensitive to the polarity of the environment. The free SPION@OA (as a colloidal suspension and as a powder) and SPION-in-HNT powder were magnetically characterized by measuring the ZFC-FC magnetization curves as well as the hysteresis cycles at 300 and 2.5 K, confirming that the super-paramagnetic behavior and the main magnetic properties of the free SPION were preserved once embedded in SPION-in-HNT.

Will temperature rise change the biochemical alterations induced in Mytilus galloprovincialis by cerium oxide nanoparticles and mercury?

It is known that, for marine coastal ecosystems, pollution and global warming are among the most threatening factors. Among emerging pollutants, nanoparticles (NPs) deserve particular attention as their possible adverse effects are significantly influenced by environmental factors such as salinity, pH and temperature, as well as by their ability to interact with other contaminants. In this framework, the present study aimed to evaluate the potential interactions between CeO2 NPs and the toxic classic metal mercury (Hg), under current and warming conditions. The marine bivalve Mytilus galloprovincialis was used as biological model and exposed to CeO2 NPs and Hg, either alone or in combination, for 28 day at 17 °C and 22 °C. A suite of biomarkers related to energetic metabolism, oxidative stress/damage, redox balance, and neurotoxicity was applied in exposed and non-exposed (control) mussels. The Hg and Ce accumulation was also assessed. Results showed that the exposure to CeO2 NPs alone did not induce toxic effects in M. galloprovincialis. On the contrary, Hg exposure determined a significant loss of energetic metabolism and a general impairment in biochemical performances. Hg accumulation in mussels was not modified by the presence of CeO2 NPs, while the biochemical alterations induced by Hg alone were partially canceled upon co-exposure with CeO2 NPs. The temperature increase induced loss of metabolic and biochemical functions and the effects of temperature prevailed on mussels exposed to pollutants acting alone or combined.

Natural molecule coatings modify the fate of cerium dioxide nanoparticles in water and their ecotoxicity to Daphnia magna.

The ongoing development of nanotechnology has raised concerns regarding the potential risk of nanoparticles (NPs) to the environment, particularly aquatic ecosystems. A relevant aspect that drives NP toxicity is represented by the abiotic and biotic processes occurring in natural matrices that modify NP properties, ultimately affecting their interactions with biological targets. Therefore, the objective of this study was to perform an ecotoxicological evaluation of CeO2NPs with different surface modifications representative of NP bio-interactions with molecules naturally occurring in the water environment, to identify the role of biomolecule coatings on nanoceria toxicity to aquatic organisms. Ad hoc synthesis of CeO2NPs with different coating agents, such as Alginate and Chitosan, was performed. The ecotoxicity of the coated CeO2NPs was assessed on the marine bacteria Aliivibrio fischeri, through the Microtox® assay, and with the freshwater crustacean Daphnia magna. Daphnids at the age of 8 days were exposed for 48 h, and several toxicity endpoints were evaluated, from the molecular level to the entire organism. Specifically, we applied a suite of biomarkers of oxidative stress and neurotoxicity and assessed the effects on behaviour through the evaluation of swimming performance. The different coatings affected the hydrodynamic behaviour and colloidal stability of the CeO2NPs in exposure media. In tap water, NPs coated with Chitosan derivative were more stable, while the coating with Alginate enhanced the aggregation and sedimentation rate. The coatings also significantly influenced the toxic effects of CeO2NPs. Specifically, in D. magna the CeO2NPs coated with Alginate triggered oxidative stress, while behavioural assays showed that CeO2NPs coated with Chitosan induced hyperactivity. Our findings emphasize the role of environmental modification in determining the NP effects on aquatic organisms.