Long-Term Toxicity of Gadolinium to the Freshwater Crustacean Daphnia magna.

The lanthanides are considered emerging contaminants but information on their long-term toxicity to aquatic species under environmentally relevant conditions is scarce. We aimed to fill this gap by evaluating the long-term adverse effects of gadolinium on the freshwater model-crustacean Daphnia magna. The exposure of D. magna for up to 39 days to 0.1 mg Gd/L (a 21-days chronic toxicity NOEC value derived by us formerly) in the lake water had no negative effect (p > 0.05) on vitality, size and reproduction of parent animals as well as their offspring. Thus, assumingly the current Gd contamination levels of surface waters pose no hazard to aquatic crustaceans that in general are very sensitive to various pollutants. Moreover, presence of 0.1 mg Gd/L in the lake water even mitigated the long-term toxic effect of 0.2 mg Ni/L (studied as a model co-contaminant) to D. magna's vitality and productivity.

Surface carboxylation or PEGylation decreases CuO nanoparticles' cytotoxicity to human cells in vitro without compromising their antibacterial properties.

Clinical use of CuO nanoparticles (NPs) as antibacterials can be hampered by their toxicity to human cells. We hypothesized that certain surface functionalizations of CuO NPs may render NPs toxic to bacteria, but still be relatively harmless to human cells. To control this hypothesis, the toxicity of differently functionalized CuO NPs to bacteria Escherichia coli vs human cells (THP-1 macrophages and HACAT keratinocytes) was compared using similar conditions and end points. CuO NPs functionalized with polyethylene glycol (CuO-PEG), carboxyl (CuO-COOH, anionic), ammonium (CuO-NH4+, cationic) and unfunctionalized CuO NPs and CuSO4 (controls) were tested. In general, the toxicity of Cu compounds decreased in the following order: CuO-NH4+ > unfunctionalized CuO > CuSO4 > CuO-COOH > CuO-PEG. Positively charged unfunctionalized CuO and especially CuO-NH4+ proved most toxic (24-h EC50 = 21.7-47 mg/l) and had comparable toxicity to bacterial and mammalian cells. The multivariate analysis revealed that toxicity of these NPs was mostly attributed to their positive zeta potential, small hydrodynamic size, high Cu dissolution, and induction of reactive oxygen species (ROS) and TNF-α. In contrast, CuO-COOH and CuO-PEG NPs had lower toxicity to human cells compared to bacteria despite efficient uptake of these NPs by human cells. In addition, these NPs did not induce TNF-α and ROS. Thus, by varying the NP functionalization and Cu form (soluble salt vs NPs), it was possible to "target" the toxicity of Cu compounds, whereas carboxylation and PEGylation rendered CuO NPs that were more toxic to bacteria than to human cells envisaging their use in medical antibacterial products.

Toxicity profiling of 24 l-phenylalanine derived ionic liquids based on pyridinium, imidazolium and cholinium cations and varying alkyl chains using rapid screening Vibrio fischeri bioassay.

A library of 24 pyridinium-, imidazolium-, and cholinium-based ionic liquids (ILs) with varying alkyl chain from C2 to C16 was toxicologically profiled using naturally luminescent marine bacteria Vibrio fischeri. The toxicity (30-min EC50) of studied ILs to Vibrio fischeri ranged from 7.82 µM (4.2 mg/L) (PyC12Phe) to 3096 µM (1227 mg/L) (ImidC2Phe), i.e. from "toxic" (EC50 1-10 mg/L) to "not harmful" (EC50 > 100 mg/L). Inhibition of the bacterial luminescence upon 30-min exposure to ILs correlated well with bacterial viability (exposure for 4 h). The toxicity of studied ILs was largely driven by the length of the alkyl chain (hydrophobicity) and not the type of cationic part of the IL: starting from C10 all the ILs irrespective of the cationic part proved "toxic". The toxicity of the studied ILs was increasing in parallel to their hydrophobicity up to log Kow = 1 (C8-C10) and then levelling up, being consistent with the previously obtained analogous data sets. The "cut-off" effect reported in this study for longer chain length members of the ILs series leads to the "limit" toxicity level for this type of ILs to be ca. 8 mM. Two open-access online tools (www.molinspiration.com and www.vcclab.org) have been applied for the calculation of the Kow values for the 24 ILs reported in this study and 21 ILs reported in the literature. This lead to plotting two nonlinear monotonic correlations between the values of experimental log (1/EC50) and calculated log Kow. The limitation of the online tools and an effect of the ILs structure on the "cut-off" effect have been discussed. The challenge of developing low microbial toxicity surface active ILs remains a significant task to overcome. Our results shed light on the new approaches for designing environmentally benign ILs and functional surfactants. As the hydrophobicity of the ILs significantly correlated with the toxicity, the Vibrio fischeri assay could be considered a powerful tool in providing toxicity data for building and evaluating the QSAR toxicity models for ILs.

Pan-European inter-laboratory studies on a panel of in vitro cytotoxicity and pro-inflammation assays for nanoparticles.

The rapid development of nanotechnologies and increased production and use of nanomaterials raise concerns about their potential toxic effects for human health and environment. To evaluate the biological effects of nanomaterials, a set of reliable and reproducible methods and development of standard operating procedures (SOPs) is required. In the framework of the European FP7 NanoValid project, three different cell viability assays (MTS, ATP content, and caspase-3/7 activity) with different readouts (absorbance, luminescence and fluorescence) and two immune assays (ELISA of pro-inflammatory cytokines IL1-ß and TNF-α) were evaluated by inter-laboratory comparison. The aim was to determine the suitability and reliability of these assays for nanosafety assessment. Studies on silver and copper oxide nanoparticles (NPs) were performed, and SOPs for particle handling, cell culture, and in vitro assays were established or adapted. These SOPs give precise descriptions of assay procedures, cell culture/seeding conditions, NPs/positive control preparation and dilutions, experimental well plate preparation, and evaluation of NPs interference. The following conclusions can be highlighted from the pan-European inter-laboratory studies: Testing of NPs interference with the toxicity assays should always be conducted. Interference tests should be designed as close as possible to the cell exposure conditions. ATP and MTS assays gave consistent toxicity results with low inter-laboratory variability using Ag and CuO NPs and different cell lines and therefore, could be recommended for further validation and standardization. High inter-laboratory variability was observed for Caspase 3/7 assay and ELISA for IL1-ß and TNF-α measurements.

An Integrated Data-Driven Strategy for Safe-by-Design Nanoparticles: The FP7 MODERN Project.

The development and implementation of safe-by-design strategies is key for the safe development of future generations of nanotechnology enabled products. The safety testing of the huge variety of nanomaterials that can be synthetized is unfeasible due to time and cost constraints. Computational modeling facilitates the implementation of alternative testing strategies in a time and cost effective way. The development of predictive nanotoxicology models requires the use of high quality experimental data on the structure, physicochemical properties and bioactivity of nanomaterials. The FP7 Project MODERN has developed and evaluated the main components of a computational framework for the evaluation of the environmental and health impacts of nanoparticles. This chapter describes each of the elements of the framework including aspects related to data generation, management and integration; development of nanodescriptors; establishment of nanostructure-activity relationships; identification of nanoparticle categories; hazard ranking and risk assessment.

Toxicity of Water Accommodated Fractions of Estonian Shale Fuel Oils to Aquatic Organisms.

Estonia is the worldwide leading producer of the fuel oils from the oil shale. We evaluated the ecotoxicity of water accommodated fraction (WAF) of two Estonian shale fuel oils ("VKG D" and "VKG sweet") to aquatic species belonging to different trophic levels (marine bacteria, freshwater crustaceans and aquatic plants). Artificial fresh water and natural lake water were used to prepare WAFs. "VKG sweet" (lower density) proved more toxic to aquatic species than "VKG D" (higher density). Our data indicate that though shale oils were very toxic to crustaceans, the short-term exposure of Daphnia magna to sub-lethal concentrations of shale fuel oils WAFs may increase the reproductive potential of survived organisms. The weak correlation between measured chemical parameters (C10-C40 hydrocarbons and sum of 16 PAHs) and WAF's toxicity to studied species indicates that such integrated chemical parameters are not very informative for prediction of shale fuel oils ecotoxicity.

Mapping the dawn of nanoecotoxicological research.

Some researchers consider nanotechnology the next industrial revolution, and consumer products and a variety of industries increasingly use synthetic nanoparticles. In this Account, we review the initial accomplishments of nanoecotoxicology, a discipline that is just a decade old. This new subdiscipline of ecotoxicology faces two important and challenging problems: the analysis of the safety of nanotechnologies in the natural environment and the promotion of sustainable development while mitigating the potential pitfalls of innovative nanotechnologies. In this Account, we provide a snapshot of the publicly available scientific information regarding the ecotoxicity of engineered nanoparticles. We pay special attention to information relevant to aquatic freshwater species commonly used for risk assessment and regulation. Just as the development of ecotoxicology has lagged behind that of toxicology, nanoecotoxicological research has developed much more slowly than nanotoxicology. Although the first nanotoxicolology papers were published in 1990s, the first nanoecotoxicology papers came out in 2006. A meta-analysis of scientific publications covering different environmental impacts of nanomaterials showed that the importance of research into the environmental impact of nanotechnology has gradually increased since 2005. Now the most frequently cited papers in the environmental disciplines are often those that focus on synthetic nanoparticles. The first nanoecotoxicology studies focused on adverse effects of nanoparticles on fish, algae and daphnids, which are ecotoxicological model organisms for classification and labeling of chemicals (these model organisms are also used in the EU chemical safety policy adopted in 2007: Registration, Evaluation, Authorization, and Restriction of Chemicals (REACH)). Based on our experience, we propose a multitrophic battery of nanoecotoxicological testing that includes particle-feeding and a priori particle-"proof" prokaryotic and eukaryotic organisms at different food-chain levels. Using this battery of selected test organisms, we demonstrated that TiO2 nanoparticles were toxic to algae and that ZnO and CuO nanoparticles were toxic to several aquatic invertebrate test species. Thus, one single biotest cannot predict the ecotoxicological effects of chemicals/nanoparticles, and researchers should use several tests instead. Moreover, produced nanoparticles usually vary in features such as size, shape, and coating; therefore, a single nanoparticle species may actually include many entities with different physicochemical properties. An ecotoxicity analysis of all these variants would require a huge number of laboratory tests. To address these issues, high throughput bioassays and computational (QSAR) models that serve as powerful alternatives to conventional (eco)toxicity testing must be implemented to handle both the diversity of nanomaterials and the complexity of ecosystems.

Potential of hyperspectral imaging microscopy for semi-quantitative analysis of nanoparticle uptake by protozoa.

Hyperspectral imaging with enhanced darkfield microscopy (HSI-M) possesses unique advantages in its simplicity and non-invasiveness. In consideration of the urgent need for profound knowledge on the behavior and effects of engineered nanoparticles (NPs), here, we determined the capability of HSI-M for examining cellular uptake of different metal-based NPs, including nanosized metals (silver and gold, both citrate stabilized), metal oxides (copper oxide and titanium dioxide), and CdSe/ZnS core/shell quantum dots at subtoxic concentrations. Specifically, we demonstrated that HSI-M can be used to detect and semi-quantify these NPs in the ciliated protozoan Tetrahymena thermophila as a model aquatic organism. Detection and semi-quantification were achieved on the basis of spectral libraries for the NPs suspended in extracellular substances secreted by this single-celled organism, accounting for matrix effects. HSI-M was able to differentiate between NP types, provided that spectral profiles were significantly different from each other. This difference, in turn, depended upon NP type, size, agglomeration status, and position relative to the focal plane. As an exception among the NPs analyzed in this study, titanium dioxide NPs showed spectral similarities compared to cell material of unexposed control cells, leading to false positives. High biological variability resulted in highly variable uptake of NPs in cells of the same sample as well as between different exposures. We therefore encourage the development of techniques able to reduce the currently long analysis times that still hamper the acquisition of statistically strong data sets. Overall, this study demonstrates the potential and challenges of HSI-M in monitoring cellular uptake of synthetic NPs.

Toxicity of Silver-Chitosan Nanocomposites to Aquatic Microcrustaceans Daphnia magna and Thamnocephalus platyurus and Naturally Luminescent Bacteria Vibrio fischeri.

All novel materials should be analyzed for their potential environmental hazard. In this study, the toxicity of different silver-chitosan nanocomposites-potential candidates for wound dressings or antimicrobial surface coatings-was evaluated using environmentally relevant aquatic microcrustaceans Daphnia magna and Thamnocephalus platyurus and naturally luminescent bacteria Vibrio fischeri. Three silver-chitosan nanocomposites (nAgCSs) with different weight ratios of Ag to CS were studied. Citrate-coated silver nanoparticles (nAg-Cit), AgNO3 (ionic control) and low molecular weight chitosan (LMW CS) were evaluated in parallel. The primary size of nAgCSs was ~50 nm. The average hydrodynamic sizes in deionized water were ≤100 nm, and the zeta potential values were positive (16-26 mV). The nAgCSs proved very toxic to aquatic crustaceans: the 48-h EC50 value for D. magna was 0.065-0.232 mg/L, and the 24-h LC50 value for T. platyurus was 0.25-1.04 mg/L. The toxic effect correlated with the shedding of Ag ions (about 1%) from nAgCSs. Upon exposure of V. fischeri to nAgCSs for 30 min, bacterial luminescence was inhibited by 50% at 13-33 mg/L. However, the inhibitory effect (minimum bactericidal concentration, MBC) on bacterial growth upon 1 h exposure was observed at higher concentrations of nAgCSs, 40-65 mg/L. LMW CS inhibited bacterial luminescence upon 30-min exposure at 5.6 mg/L, but bacterial growth was inhibited at a much higher concentration (1 h MBC > 100 mg/L). The multi-trophic test battery, where D. magna was the most sensitive test organism, ranked the silver-chitosan nanocomposites from 'extremely toxic' [L(E)C50 ≤ 0.1 mg/L] to 'very toxic' [L(E)C50 > 0.1-1 mg/L]. Chitosan was toxic (EC(L)50) to crustaceans at ~12 mg/L, and ranked accordingly as 'harmful' [L(E)C50 > 10-100 mg/L]. Thus, silver-chitosan nanocomposites may pose a hazard to aquatic organisms and must be handled accordingly.

Toxicity of CuO nanoparticles to yeast Saccharomyces cerevisiae BY4741 wild-type and its nine isogenic single-gene deletion mutants.

A suite of eight tentatively oxidative stress response-deficient Saccharomyces cerevisiae BY4741 single-gene mutants (sod1Δ, sod2Δ, yap1Δ, cta1Δ, ctt1Δ, gsh1Δ, glr1Δ, and ccs1Δ) and one copper-vulnerable mutant (cup2Δ) was used to elucidate weather the toxicity of CuO nanoparticles to S. cerevisiae is mediated by oxidative stress (OS). Specifically, sensitivity profiles of mutants' phenotypes and wild-type (wt) upon exposure to nano-CuO were compared. As controls, CuSO4 (solubility), bulk-CuO (size), H2O2, and menadione (OS) were used. Growth inhibition of wt and mutant strains was studied in rich YPD medium and cell viability in deionized water (DI). Dissolved Cu-ions were quantified by recombinant metal-sensing bacteria and chemical analysis. To wt strain nano-CuO was 32-fold more toxic than bulk-CuO: 24-h IC50 4.8 and 155 mg/L in DI and 643 and >20000 mg/L in YPD, respectively. In toxicant-free YPD medium, all mutants had practically similar growth patterns as wt. However, the mutant strains sod1Δ, sod2Δ, ccs1Δ, and yap1Δ showed up to 12-fold elevated sensitivity toward OS standard chemicals menadione and H2O2 but not to nano-CuO, indicating that CuO nanoparticles exerted toxicity to yeast cells via different mechanisms. The most vulnerable strain to all studied Cu compounds was the copper stress response-deficient strain cup2Δ (∼16-fold difference with wt), indicating that the toxic effect of CuO (nano)particles proceeds via dissolved Cu-ions. The dissolved copper solely explained the toxicity of nano-CuO in DI but not in YPD. Assumingly, in YPD nano-CuO acquired a coating of peptides/proteins and sorbed onto the yeast's outer surface, resulting in their increased solubility in the close vicinity of yeast cells and increased uptake of Cu-ions that was not registered by the assays used for the analysis of dissolved Cu-ions in the test medium. Lastly, as yeast retained its viability in DI even by 24th hour of incubation, the profiling of the acute basal toxicity of chemicals toward yeasts may be conducted in DI.

Interaction of firefly luciferase and silver nanoparticles and its impact on enzyme activity.

We report on the dose-dependent inhibition of firefly luciferase activity induced by exposure of the enzyme to 20 nm citrate-coated silver nanoparticles (AgNPs). The inhibition mechanism was examined by characterizing the physicochemical properties and biophysical interactions of the enzyme and the AgNPs. Consistently, binding of the enzyme induced an increase in zeta potential from -22 to 6 mV for the AgNPs, triggered a red-shift of 44 nm in the absorbance peak of the AgNPs, and rendered a 'protein corona' of 20 nm in thickness on the nanoparticle surfaces. However, the secondary structures of the enzyme were only marginally affected upon formation of the protein corona, as verified by circular dichroism spectroscopy measurement and multiscale discrete molecular dynamics simulations. Rather, inductively coupled plasma mass spectrometry measurement revealed a significant ion release from the AgNPs. The released silver ions could readily react with the cysteine residues and N-groups of the enzyme to alter the physicochemical environment of their neighboring catalytic site and subsequently impair the enzymatic activity.

Toxicity of Ag, CuO and ZnO nanoparticles to selected environmentally relevant test organisms and mammalian cells in vitro: a critical review.

Nanoparticles (NPs) of copper oxide (CuO), zinc oxide (ZnO) and especially nanosilver are intentionally used to fight the undesirable growth of bacteria, fungi and algae. Release of these NPs from consumer and household products into waste streams and further into the environment may, however, pose threat to the 'non-target' organisms, such as natural microbes and aquatic organisms. This review summarizes the recent research on (eco)toxicity of silver (Ag), CuO and ZnO NPs. Organism-wise it focuses on key test species used for the analysis of ecotoxicological hazard. For comparison, the toxic effects of studied NPs toward mammalian cells in vitro were addressed. Altogether 317 L(E)C50 or minimal inhibitory concentrations (MIC) values were obtained for algae, crustaceans, fish, bacteria, yeast, nematodes, protozoa and mammalian cell lines. As a rule, crustaceans, algae and fish proved most sensitive to the studied NPs. The median L(E)C50 values of Ag NPs, CuO NPs and ZnO NPs (mg/L) were 0.01, 2.1 and 2.3 for crustaceans; 0.36, 2.8 and 0.08 for algae; and 1.36, 100 and 3.0 for fish, respectively. Surprisingly, the NPs were less toxic to bacteria than to aquatic organisms: the median MIC values for bacteria were 7.1, 200 and 500 mg/L for Ag, CuO and ZnO NPs, respectively. In comparison, the respective median L(E)C50 values for mammalian cells were 11.3, 25 and 43 mg/L. Thus, the toxic range of all the three metal-containing NPs to target- and non-target organisms overlaps, indicating that the leaching of biocidal NPs from consumer products should be addressed.

Synergistic antibacterial effect of copper and silver nanoparticles and their mechanism of action.

Bacterial infections are one of the leading causes of death worldwide. In the case of topical bacterial infections such as wound infections, silver (Ag) has historically been one of the most widely used antibacterials. However, scientific publications have demonstrated the adverse effects of silver on human cells, ecotoxicity and insufficient antibacterial effect for the complete elimination of bacterial infections. The use of Ag in the form of nanoparticles (NPs, 1-100 nm) allows to control the release of antibacterial Ag ions but is still not sufficient to eliminate infection and avoid cytotoxicity. In this study, we tested the potency of differently functionalized copper oxide (CuO) NPs to enhance the antibacterial properties of Ag NPs. The antibacterial effect of the mixture of CuO NPs (CuO, CuO-NH2 and CuO-COOH NPs) with Ag NPs (uncoated and coated) was studied. CuO and Ag NP combinations were more efficient than Cu or Ag (NPs) alone against a wide range of bacteria, including antibiotic-resistant strains such as gram-negative Escherichia coli and Pseudomonas aeruginosa as well as gram-positive Staphylococcus aureus, Enterococcus faecalis and Streptococcus dysgalactiae. We showed that positively charged CuO NPs enhanced the antibacterial effect of Ag NPs up to 6 times. Notably, compared to the synergy of CuO and Ag NPs, the synergy of respective metal ions was low, suggesting that NP surface is required for the enhanced antibacterial effect. We also studied the mechanisms of synergy and showed that the production of Cu+ ions, faster dissolution of Ag+ from Ag NPs and lower binding of Ag+ by proteins of the incubation media in the presence of Cu2+ were the main mechanisms of the synergy. In summary, CuO and Ag NP combinations allowed increasing the antibacterial effect up to 6 times. Thus, using CuO and Ag NP combinations enables to retain excellent antibacterial effects due to Ag and synergy and enhances beneficial effects, since Cu is a vital microelement for human cells. Thus, we suggest using combinations of Ag and CuO NPs in antibacterial materials, such as wound care products, to increase the antibacterial effect of Ag, improve safety and prevent and cure topical bacterial infections.

Comparison of Toxicity and Cellular Uptake of CdSe/ZnS and Carbon Quantum Dots for Molecular Tracking Using Saccharomyces cerevisiae as a Fungal Model.

Plant resource sharing mediated by mycorrhizal fungi has been a subject of recent debate, largely owing to the limitations of previously used isotopic tracking methods. Although CdSe/ZnS quantum dots (QDs) have been successfully used for in situ tracking of essential nutrients in plant-fungal systems, the Cd-containing QDs, due to the intrinsic toxic nature of Cd, are not a viable system for larger-scale in situ studies. We synthesized amino acid-based carbon quantum dots (CQDs; average hydrodynamic size 6 ± 3 nm, zeta potential -19 ± 12 mV) and compared their toxicity and uptake with commercial CdSe/ZnS QDs that we conjugated with the amino acid cysteine (Cys) (average hydrodynamic size 308 ± 150 nm, zeta potential -65 ± 4 mV) using yeast Saccharomyces cerevisiae as a proxy for mycorrhizal fungi. We showed that the CQDs readily entered yeast cells and were non-toxic up to 100 mg/L. While the Cys-conjugated CdSe/ZnS QDs were also not toxic to yeast cells up to 100 mg/L, they were not taken up into the cells but remained on the cell surfaces. These findings suggest that CQDs may be a suitable tool for molecular tracking in fungi (incl. mychorrhizal fungi) due to their ability to enter fungal cells.

Upon exposure to Cu nanoparticles, accumulation of copper in the isopod Porcellio scaber is due to the dissolved Cu ions inside the digestive tract.

The fate of nanoparticles in organisms is of significant interest. In the current work, we used a test system with terrestrial isopods (Porcellio scaber) fed with food spiked with Cu NPs or soluble Cu salt for 14 days. Two different doses were used for spiking to yield final concentrations of 2000 and 5000 µg Cu/g dry food. After the exposure period, part of the exposed group of animals was transferred to clean food to depurate. Cu content was analyzed in the digestive glands, gut, and the 'rest' of the body. Similar patterns of (i) assimilated and depurated amounts of Cu, (ii) Cu body distribution, and (iii) effect on isopods feeding behavior were observed regardless of whether the animals were fed with Cu NPs or soluble Cu salt spiked food. Thus, Cu ions and not Cu NPs were assimilated by the digestive gland cells. Solubilization of the Cu NPs applied to the leaves was also analyzed with chemical methods and recombinant Cu-sensing bacteria. The comparison of the in vitro data on solubilization of Cu NPs and in vivo data on Cu accumulation in the animal tissues showed that about 99% of accumulated copper ions was dissolved from ingested Cu NPs in the digestive system of isopods.

Virgin and UV-weathered polyamide microplastics posed no effect on the survival and reproduction of Daphnia magna.

Although evidence suggests that microplastic (MP) particles pose a risk to organisms, the effects of virgin and weathered MP should be evaluated separately as their effects may be different. In this work, we provide new information on the toxic potential of virgin and UV-weathered polyamide, one of the commonly used plastics worldwide. Polyamide MP particles were subjected to UV-weathering in wet conditions over 26 days in a customized irradiation chamber equipped with UV-C light tubes (15 W each, max. wavelength 254 nm). The toxicity of virgin and UV-weathered polyamide MP (< 180 µm in one dimension, 100 and 300 mg L-1) was evaluated by studying Daphnia magna reproduction in natural lake water spiked with MP, following the 21-day OECD 211 test guideline. In parallel, a nonionic surfactant Tween 20 (7 mg L-1) was added to the test medium to improve the suspendability of the MP. The results of the tests showed no adverse effects of either virgin or UV-weathered polyamide MP on the reproduction of D. magna. In addition, presence of Tween 20 in the test medium had no effects on the test results. These results bring a new perspective on the potential long-term impact of polyamide particles on aquatic organisms, especially considering that the polyamide has received marginal attention in the ecotoxicological research. However, standard test endpoints (survival and reproduction) may still miss long-term adverse effects of insoluble e.g., plastic particles and additional studies may be necessary.

Nanomaterials and Microorganisms: From Green Synthesis to Antibacterial Applications in Medicine and Agriculture.

Nanomaterial-based solutions for microorganism-related issues are gaining interest in medical fields, consumer applications, and agriculture [...].

Polyamide microplastic exposure elicits rapid, strong and genome-wide evolutionary response in the freshwater non-biting midge Chironomus riparius.

Susceptibility to hazardous materials and contamination is largely determined by genetic make-up and evolutionary history of affected organisms. Yet evolutionary adaptation and microevolutionary processes triggered by contaminants are rarely considered in ecotoxicology. Using an evolve and resequencing approach, we investigated genome-wide responses of the midge C. riparius exposed to virgin polyamide microplastics (0-180 µm size range, at concentration 1 g kg-1) during seven consecutive generations. The results were integrated to a parallel life-cycle experiment ran under the same exposure conditions. Emergence, life-cycle trait, showed first a substantial reduction in larval survival, followed by a rapid recovery within three generations. On the genomic level, we observed substantial selectively driven allele frequency changes (mean 0.566 ± 0.0879) within seven generations, associated with a mean selection coefficient of 0.322, indicating very strong selection pressure. Putative selection targets were mainly connected to oxidative stress in the microplastics exposed C. riparius population. This is the first multigenerational study on chironomids to provide evidence that upon exposure to polyamide microplastic there are changes on the genomic level, providing basis to rapid adaptation of aquatic organisms to microplastics.

Aminocatalysts are More Environmentally Friendly than Hydrogen-Bonding Catalysts.

The importance of asymmetric organocatalysis in contemporary organic synthesis is widely acknowledged. However, there are practically no data on the environmental safety of organocatalysts, although this aspect is crucial for the sustainability of all new materials, chemicals, and technologies. To start to fill this data-gap, a library of 26 organocatalysts containing hydrogen-bonding catalysts [(thio)ureas and squaramides] and aminocatalysts (primary or secondary amines) was evaluated for their toxicity using the naturally luminescent Vibrio fischeri bacteria (ISO assay; one of the most widely used ecotoxicity tests). Thioureas and squaramides were shown to be relatively toxic: none of them was ranked as "not harmful" (i. e., half maximal effective concentration EC50 >100 mg L-1 ), whereas the presence of the trifluoromethyl moiety increased their toxic effect. Importantly, the aminocatalysts, whose EC50 values ranged from 25 to >300 mg L-1 , could be considered remarkably more environmentally safe or green alternatives.

Visible-Light Active Flexible and Durable Photocatalytic Antibacterial Ethylene-co-vinyl Acetate-Ag/AgCl/α-Fe2O3 Composite Coating.

When particles are mixed in polymer, particle surfaces become passivated by polymer matrix, leading to significantly reduced photocatalytic and, thus, also reduced antibacterial activity, as the catalytic particles become isolated from the outer environment and microorganisms reaching the surface. Herein, we demonstrate a facile and rapid approach for coating preparation at room temperature, yielding good adhesion of particles in combination with the particles' interface location. Flexible ethylene-co-vinyl acetate Ag/AgCl/α-Fe2O3 composite coatings were prepared by the spin-coating method. The synthesized photocatalytically active coating surface exhibited a distinct and rapid inhibition of bacterial growth, with at least a 7-log reduction of gram-positive bacteria Staphylococcus aureus viability after 30 min of visible-light illumination. We also analyzed the shedding of the Ag-ions and reactive oxygen species production from the composite coating and showed that reactive oxygen species played the main role in the photocatalytic bacterial inactivation, destroying the bacteria cell as proven by the Confocal Laser Scanning Microscopy.