ABSTRACT
Marine biofouling negatively impacts industries with off-shore infrastructures, such as naval, oil, and aquaculture. To date, there are no ideal sustainable, economic, and environmentally benign solutions to deal with this phenomenon. The advances achieved in green solvents, as well as its application in different industries, such as pharmaceutical and biotechnology, have promoted the emergence of deep eutectic systems (DES). These eutectic systems have applications in various fields and can be revolutionary in the marine-based industrial sector. In this study, the main objective was to investigate the potential use of hydrophobic DES (HDES) based on menthol and natural organic acids for their use as marine antifouling coatings. Our strategy encompassed the physicochemical characterization of different formulations, which allowed us to identify the most appropriate molar ratio and intermolecular interactions for HDES formations. The miscibility of the resulting HDES with the marine coating has been evaluated and proven to be successful. The Men/OL (1:1) system proved to be the most promising in terms of cost-production and thus was the one used in subsequent antifouling tests. The cytotoxicity of this HDES was evaluated using an in vitro cell model (HaCat cells) showing no significant toxicity. Furthermore, the application of this system incorporated into coatings that are used in marine structures was also studied using marine species (Mytilus edulis mussels and Patella vulgata limpets) to evaluate both their antifouling and ecotoxicity effects. HDES Men/OL (1:1) incorporated in marine coatings was promising in reducing marine macrofouling and also proved to be effective at the level of microfouling without viability impairment of the tested marine species. It was revealed to be more efficient than using copper oxide, metallic copper, or ivermectin as antifouling agents. Biochemical assays performed on marine species showed that this HDES does not induce oxidative stress in the tested species. These results are a strong indication of the potential of this HDES to be sustainable and efficiently used in marine fouling control technologies.
ABSTRACT
Natural deep eutectic solvents (NADESs) are considered as green solvents, and due to their promising sustainability, they have been applied in many research fields. In this study, the main goal is to use various NADES systems to replace the traditional solvents used in conservation and restoration to remove varnish layers in a painting. The toxicity of traditional solvents, such as toluene or acetone, is well known in the chemistry field. To replace them, it is important to understand the intrinsic physicochemical properties of a solvent that may act as a substitute. Polarity and solubility are proposed as the best parameters required for this study. The Nile red probe was used to confirm the similarity between the polarity of deep eutectic systems (DESs) and traditional solvents. According to their polarities and Hansen solubility parameters, it is possible to predict the best solvents to solubilize the natural resin varnishes. Besides this, some arithmetic models can also be applied to estimate the critical or thermodynamic properties, which are useful tools to predict the behavior of these solvents. We have further proven the possibility of dissolving natural varnishes such as dammar or mastic in hydrophobic DESs, such as menthol + lauric acid, menthol + decanoic acid, or menthol + thymol.
