RESUMO
Mesoporous silica engineered nanomaterials are of interest to the industry due to their drug-carrier ability. Advances in coating technology include using mesoporous silica nanocontainers (SiNC) loaded with organic molecules as additives in protective coatings. The SiNC loaded with the biocide 4,5-dichloro-2-octyl-4-isothiazolin-3-one (DCOIT), i.e., SiNC-DCOIT, is proposed as an additive for antifouling marine paints. As the instability of nanomaterials in ionic-rich media has been reported and related to shifting key properties and its environmental fate, this study aims at understanding the behaviour of SiNC and SiNC-DCOIT in aqueous media with distinct ionic strengths. Both nanomaterials were dispersed in (i) low- (ultrapure water-UP) and (ii) high- ionic strength media-artificial seawater (ASW) and f/2 medium enriched in ASW (f/2 medium). The morphology, size and zeta potential (ζP) of both engineering nanomaterials were evaluated at different timepoints and concentrations. Results showed that both nanomaterials were unstable in aqueous suspensions, with the initial ζP values in UP below -30 mV and the particle size varying from 148 to 235 nm and 153 to 173 nm for SiNC and SiNC-DCOIT, respectively. In UP, aggregation occurs over time, regardless of the concentration. Additionally, the formation of larger complexes was associated with modifications in the ζP values towards the threshold of stable nanoparticles. In ASW, SiNC and SiNC-DCOIT formed aggregates (<300 nm) independently of the time or concentration, while larger and heterogeneous nanostructures (>300 nm) were detected in the f/2 medium. The pattern of aggregation detected may increase engineering nanomaterial sedimentation rates and enhance the risks towards dwelling organisms.
RESUMO
Corrosion is an environmental and economic global problem. "Smart" or stimuli-responsive colorimetric nanosensors for maritime coatings have been proposed as an asset to overcome the limitations of the current monitoring techniques by changing color in the presence of triggers associated with the early stages of corrosion. Layered double hydroxides (Zn-Al LDH; Mg-Al LDH) and silica mesoporous nanocapsules (SiNC) were used as precursor nanocarriers of active compounds: hexacyanoferrate ions ([Fe(CN)6]3-) and phenolphthalein (PhPh), respectively. Additionally, the safer-by-design principles were employed to optimize the nanosensors in an eco-friendly perspective (e.g., regular vs. warm-washed SiNC-PhPh; immobilization using different carriers: Zn-Al LDH-[Fe(CN)6]3- vs. Mg-Al LDH-[Fe(CN)6]3-). Therefore, the present study aims to assess the environmental behavior in saltwater and the toxic effects of the nanosensors, their nanocarriers, and the active compounds on the marine microalgae Tetraselmis chuii and the crustacean Artemia salina. Briefly, tested compounds exhibited no acute toxic effects towards A. salina (NOEC = 100 mg/L), apart from SiNC-PhPh (LC50 = 2.96 mg/L) while tested active compounds and nanosensors caused significant growth inhibition on T. chuii (lowest IC50 = 0.40 mg/L for SiNC-PhPh). The effects of [Fe(CN)6]3- were similar regardless of the nanocarrier choice. Regarding SiNC-PhPh, its toxicity can be decreased at least twice by simply reinforcing the nanocapsules washing, which contributes to the removal (at least partially) of the surfactants residues. Thus, implementing safe-by-design strategies in the early stages of research proved to be critical, although further progress is still needed towards the development of truly eco-friendly nanosensors.
