Efficacy and Ecotoxicity of Novel Anti-Fouling Nanomaterials in Target and Non-Target Marine Species.

Biofouling is a global problem that affects virtually all the immersed structures. Currently, several novel environmentally friendly approaches are being tested worldwide to decrease the toxicity of biocides in non-fouling species, such as the encapsulation/immobilization of commercially available biocides, in order to achieve control over the leaching rate. The present study addresses the toxicity of two widely used booster biocides, zinc pyrithione (ZnPT) and copper pyrithione (CuPT), in its free and incorporated forms in order to assess their toxicity and anti-fouling efficacy in target and non-target species. To achieve this goal, the following marine organisms were tested; the green microalgae Tetraselmis chuii (non-target species) and both target species, the diatom Phaeodactylum tricornutum and the mussel Mytilus edulis. Organisms were exposed to both biocides, two unloaded nanostructured materials and nanomaterials loaded with biocides, from 10 µg/L to 100 mg/L total weight, following standard protocols. The most eco-friendly and simultaneously efficient anti-fouling solution against the two photosynthetic species (nanoclays loaded with ZnPT) was then tested on mussels to assess its lethal efficacy (LC50 = 123 µg/L) and compared with free biocide (LC50 = 211 µg/L) and unloaded material (LC50 > 1000 µg/L). A second exposure test with sub-lethal concentrations (lower than 100 µg/L), using mussels, was carried out to assess biochemical changes caused by the tested compounds. Oxidative stress, detoxification and neurotransmission markers were not responsive; however, different antioxidant patterns were found with free ZnPT and loaded nanoclay exposures. Thus, the immobilization of the biocide ZnPT into nanoclays proved to be a promising efficient and eco-friendly anti-fouling strategy.

Metabolomics of silver nanoparticles toxicity in HaCaT cells: structure-activity relationships and role of ionic silver and oxidative stress.

The widespread use of silver nanoparticles (AgNPs) is accompanied by a growing concern regarding their potential risks to human health, thus calling for an increased understanding of their biological effects. The aim of this work was to systematically study the extent to which changes in cellular metabolism were dependent on the properties of AgNPs, using NMR metabolomics. Human skin keratinocytes (HaCaT cells) were exposed to citrate-coated AgNPs of 10, 30 or 60 nm diameter and to 30 nm AgNPs coated either with citrate (CIT), polyethylene glycol (PEG) or bovine serum albumin (BSA), to assess the influence of NP size and surface chemistry. Overall, CIT-coated 60 nm and PEG-coated 30 nm AgNPs had the least impact on cell viability and metabolism. The role of ionic silver and reactive oxygen species (ROS)-mediated effects was also studied, in comparison to CIT-coated 30 nm particles. At concentrations causing an equivalent decrease in cell viability, Ag(+ )ions produced a change in the metabolic profile that was remarkably similar to that seen for AgNPs, the main difference being the lesser impact on the Krebs cycle and energy metabolism. Finally, this study newly reported that while down-regulated glycolysis and disruption of energy production were common to AgNPs and H2O2, the impact on some metabolic pathways (GSH synthesis, glutaminolysis and the Krebs cycle) was independent of ROS-mediated mechanisms. In conclusion, this study shows the ability of NMR metabolomics to define subtle biochemical changes induced by AgNPs and demonstrates the potential of this approach for rapid, untargeted screening of pre-clinical toxicity of nanomaterials in general.

Control of crystallite and particle size in the synthesis of layered double hydroxides: Macromolecular insights and a complementary modeling tool.

Zinc-aluminum layered double hydroxides with nitrate intercalated (Zn(n)Al-NO3, n=Zn/Al) is an intermediate material for the intercalation of different functional molecules used in a wide range of industrial applications. The synthesis of Zn(2)Al-NO3 was investigated considering the time and temperature of hydrothermal treatment. By examining the crystallite size in two different directions, hydrodynamic particle size, morphology, crystal structure and chemical species in solution, it was possible to understand the crystallization and dissolution processes involved in the mechanisms of crystallite and particle growth. In addition, hydrogeochemical modeling rendered insights on the speciation of different metal cations in solution. Therefore, this tool can be a promising solution to model and optimize the synthesis of layered double hydroxide-based materials for industrial applications.

One-pot synthesis of triangular gold nanoplates allowing broad and fine tuning of edge length.

A photocatalytic approach was used to synthesize triangular nanoplates in aqueous solution. The synthesis is based on the reduction of a gold salt using a tin(iv) porphyrin as photocatalyst, cetyltrimethylammonium bromide (CTAB) as a stabilizing agent, and triethanolamine (TEA) as the final electron donor. The average edge length of the triangular nanoplates can be easily changed in the range 45-250 nm by varying the concentration of photocatalyst, and fine-tuning of the average edge length is achieved by varying the concentration of CTAB. Study of the mechanism of formation of the nanoplates by UV-vis and by transmission electron microscopy (TEM) shows that there is a first stage where formation of 5 nm seeds takes place, further growth is probably by fusion and by direct reduction of gold onto the preformed nanoparticles. The nanoparticles formed during the photocatalytic reduction of the gold precursor show an irregular shape that evolves to regular triangular nanoplates after ripening in solution for 24 h.