Daphnia as a model organism to probe biological responses to nanomaterials-from individual to population effects via adverse outcome pathways.

The importance of the cladoceran Daphnia as a model organism for ecotoxicity testing has been well-established since the 1980s. Daphnia have been increasingly used in standardised testing of chemicals as they are well characterised and show sensitivity to pollutants, making them an essential indicator species for environmental stress. The mapping of the genomes of D. pulex in 2012 and D. magna in 2017 further consolidated their utility for ecotoxicity testing, including demonstrating the responsiveness of the Daphnia genome to environmental stressors. The short lifecycle and parthenogenetic reproduction make Daphnia useful for assessment of developmental toxicity and adaption to stress. The emergence of nanomaterials (NMs) and their safety assessment has introduced some challenges to the use of standard toxicity tests which were developed for soluble chemicals. NMs have enormous reactive surface areas resulting in dynamic interactions with dissolved organic carbon, proteins and other biomolecules in their surroundings leading to a myriad of physical, chemical, biological, and macromolecular transformations of the NMs and thus changes in their bioavailability to, and impacts on, daphnids. However, NM safety assessments are also driving innovations in our approaches to toxicity testing, for both chemicals and other emerging contaminants such as microplastics (MPs). These advances include establishing more realistic environmental exposures via medium composition tuning including pre-conditioning by the organisms to provide relevant biomolecules as background, development of microfluidics approaches to mimic environmental flow conditions typical in streams, utilisation of field daphnids cultured in the lab to assess adaption and impacts of pre-exposure to pollution gradients, and of course development of mechanistic insights to connect the first encounter with NMs or MPs to an adverse outcome, via the key events in an adverse outcome pathway. Insights into these developments are presented below to inspire further advances and utilisation of these important organisms as part of an overall environmental risk assessment of NMs and MPs impacts, including in mixture exposure scenarios.

Nanotoxicity of Graphene Oxide - Gold Nanohybrid to Daphnia magna.

The expanding use of hybrid nanomaterials in many applications necessitates evaluation of their environmental risks. This study investigates the acute toxicity and bioaccumulation of graphene oxide - gold (GO-Au) nanohybrid in neonates (<24 hrs old) of Daphnia magna after exposure to a wide range of concentrations (1-100 mg/L). No significant mortality or immobilisation was observed after the exposure period. Microscopic observation showed an uptake of the nanohybrid and internal damage in the gut of the exposed organisms. Bioaccumulation of the GO-Au nanohybrid also occurred in a concentration-dependant manner. Continuous evaluation of the environmental risks from exposure to this nanohybrid and other advanced materials is imperative to avert disruption to the ecosystem.

Co-exposure of carbon nanotubes with carbofuran pesticide affects metabolic rate in Palaemon pandaliformis (shrimp).

Palaemon pandalirformis (shrimp) is a species widely distributed in the Brazilian coastal region and with an important economic role. In addition, this organism is considered an indicator of environmental pollution in estuaries; however, its physiological responses to toxic environmental pollutants, including pesticides and nanomaterials, are not well known, mainly, the effects of co-exposure. Thus, the purpose of this study was to evaluate the ecotoxicological effects of co-exposure between oxidized multiwalled carbon nanotubes (HNO3-MWCNT) and carbofuran pesticide on the routine metabolism of P. pandalirformis. The shrimps were exposed to different concentrations of HNO3-MWCNT (0; 10; 100; 500; 1000 µg L-1), carbofuran (0; 0.1; 1.0; 5.0; 10 µg L-1) and to co-exposure with 100 µg L-1 of HNO3-MWCNT + carbofuran (0; 0.1; 1.0; 5.0; 10 µg L-1), to evaluate the effects on metabolic rate (O2 consumption) and excretion of ammonia (NH4+NH3). Our results showed that the shrimps exposed to HNO3-MWCNT (10 µg L-1) increased the metabolic rate by 292% and the excretion of ammonia by 275%; those exposed to carbofuran (10 µg L-1) increased their metabolic rate by 162% and the excretion of ammonia by 425%; and with the co-exposure of HNO3-MWCNT + carbofuran there was also an increase in the metabolic rate by 317% and an excretion of ammonia by 433% when compared to control. These findings provides useful information toward better understanding the physiological responses of shrimps after combined exposure to nanomaterials and pesticides in aquatic environments.

Synthesis and Characterisation of a Graphene Oxide-Gold Nanohybrid for Use as Test Material.

This paper reports the synthesis and characterization of a graphene oxide-gold nanohybrid (GO-Au) and evaluates its suitability as a test material, e.g., in nano(eco)toxicological studies. In this study, we synthesised graphene oxide (GO) and used it as a substrate for the growth of nano-Au decorations, via the chemical reduction of gold (III) using sodium citrate. The GO-Au nanohybrid synthesis was successful, producing AuNPs (~17.09 ± 4.6 nm) that were homogenously distributed on the GO sheets. They exhibited reproducible characteristics when characterised using UV-Vis, TGA, TEM, FTIR, AFM, XPS and Raman spectroscopy. The nanohybrid also showed good stability in different environmental media and its physicochemical characteristics did not deteriorate over a period of months. The amount of Au in each of the GO-Au nanohybrid samples was highly comparable, suggesting a potential for use as chemical label. The outcome of this research represents a crucial step forward in the development of a standard protocol for the synthesis of GO-Au nanohybrids. It also paves the way towards a better understanding of the nanotoxicity of GO-Au nanohybrid in biological and environmental systems.

Conformational analysis of tannic acid: Environment effects in electronic and reactivity properties.

Polyphenols are natural molecules of crucial importance in many applications, of which tannic acid (TA) is one of the most abundant and established. Most high-value applications require precise control of TA interactions with the system of interest. However, the molecular structure of TA is still not comprehended at the atomic level, of which all electronic and reactivity properties depend. Here, we combine an enhanced sampling global optimization method with density functional theory (DFT)-based calculations to explore the conformational space of TA assisted by unsupervised machine learning visualization and then investigate its lowest energy conformers. We study the external environment's effect on the TA structure and properties. We find that vacuum favors compact structures by stabilizing peripheral atoms' weak interactions, while in water, the molecule adopts more open conformations. The frontier molecular orbitals of the conformers with the lowest harmonic vibrational free energy have a HOMO-LUMO energy gap of 2.21 (3.27) eV, increasing to 2.82 (3.88) eV in water, at the DFT generalized gradient approximation (and hybrid) level of theory. Structural differences also change the distribution of potential reactive sites. We establish the fundamental importance of accurate structural consideration in determining TA and related polyphenol interactions in relevant technological applications.

Recent Advances in Immunosafety and Nanoinformatics of Two-Dimensional Materials Applied to Nano-imaging.

Two-dimensional (2D) materials have emerged as an important class of nanomaterials for technological innovation due to their remarkable physicochemical properties, including sheet-like morphology and minimal thickness, high surface area, tuneable chemical composition, and surface functionalization. These materials are being proposed for new applications in energy, health, and the environment; these are all strategic society sectors toward sustainable development. Specifically, 2D materials for nano-imaging have shown exciting opportunities in in vitro and in vivo models, providing novel molecular imaging techniques such as computed tomography, magnetic resonance imaging, fluorescence and luminescence optical imaging and others. Therefore, given the growing interest in 2D materials, it is mandatory to evaluate their impact on the immune system in a broader sense, because it is responsible for detecting and eliminating foreign agents in living organisms. This mini-review presents an overview on the frontier of research involving 2D materials applications, nano-imaging and their immunosafety aspects. Finally, we highlight the importance of nanoinformatics approaches and computational modeling for a deeper understanding of the links between nanomaterial physicochemical properties and biological responses (immunotoxicity/biocompatibility) towards enabling immunosafety-by-design 2D materials.

Mitigation of graphene oxide toxicity in C. elegans after chemical degradation with sodium hypochlorite.

Graphene oxide (GO) is a promising and strategic carbon-based nanomaterial for innovative and disruptive technologies. It is therefore essential to address its environmental health and safety aspects. In this work, we evaluated the chemical degradation of graphene oxide by sodium hypochlorite (NaClO, bleach water) and its consequences over toxicity, on the nematode Caenorhabditis elegans. The morphological, chemical, and structural properties of GO and its degraded product, termed NaClO-GO, were characterized, exploring an integrated approach. After the chemical degradation of GO at room temperature, its flake size was reduced from 156 to 29 nm, while NaClO-GO showed changes in UV-vis absorption, and an increase in the amount of oxygenated surface groups, which dramatically improved its colloidal stability in moderately hard reconstituted water (EPA medium). Acute and chronic exposure endpoints (survival, growth, fertility, and reproduction) were monitored to evaluate material toxicities. NaClO-GO presented lower toxicity at all endpoints. For example, an increase of over 100% in nematode survival was verified for the degraded material when compared to GO at 10 mg L-1. Additionally, enhanced dark-field hyperspectral microscopy confirmed the oral uptake of both materials by C. elegans. Finally, this work represents a new contribution toward a better understanding of the links between the transformation of graphene-based materials and nanotoxicity effects (mitigation), which is mandatory for the safety improvements that are required to maximize nanotechnological benefits to society.

Graphene oxide-silver nanoparticle hybrid material: an integrated nanosafety study in zebrafish embryos.

This work reports an integrated nanosafety study including the synthesis and characterization of the graphene oxide-silver nanoparticle hybrid material (GO-AgNPs) and its nano-ecotoxicity evaluation in the zebrafish embryo model. The influences of natural organic matter (NOM) and a chorion embryo membrane were considered in this study, looking towards more environmentally realistic scenarios and standardized nanotoxicity testing. The nanohybrid was successfully synthesized using the NaBH4 aqueous method, and AgNPs (~ 5.8 nm) were evenly distributed over the GO surface. GO-AgNPs showed a dose-response acute toxicity: the LC50 was 1.5 mg L-1 for chorionated embryos. The removal of chorion, however, increased this toxic effect by 50%. Furthermore, the presence of NOM mitigated mortality, and LC50 for GO-AgNPs changed respectively from 2.3 to 1.2 mg L-1 for chorionated and de-chorionated embryos. Raman spectroscopy confirmed the ingestion of GO by embryos; but without displaying acute toxicity up to 100 mg L-1, indicating that the silver drove toxicity down. Additionally, it was observed that silver nanoparticle dissolution has a minimal effect on these observed toxicity results. Finally, understanding the influence of chorion membranes and NOM is a critical step towards the standardization of testing for zebrafish embryo toxicity in safety assessments and regulatory issues.

Effect of the Albumin Corona on the Toxicity of Combined Graphene Oxide and Cadmium to Daphnia magna and Integration of the Datasets into the NanoCommons Knowledge Base.

In this work, we evaluated the effect of protein corona formation on graphene oxide (GO) mixture toxicity testing (i.e., co-exposure) using the Daphnia magna model and assessing acute toxicity determined as immobilisation. Cadmium (Cd2+) and bovine serum albumin (BSA) were selected as co-pollutant and protein model system, respectively. Albumin corona formation on GO dramatically increased its colloidal stability (ca. 60%) and Cd2+ adsorption capacity (ca. 4.5 times) in reconstituted water (Daphnia medium). The acute toxicity values (48 h-EC50) observed were 0.18 mg L-1 for Cd2+-only and 0.29 and 0.61 mg L-1 following co-exposure of Cd2+ with GO and BSA@GO materials, respectively, at a fixed non-toxic concentration of 1.0 mg L-1. After coronation of GO with BSA, a reduction in cadmium toxicity of 110 % and 238% was achieved when compared to bare GO and Cd2+-only, respectively. Integration of datasets associated with graphene-based materials, heavy metals and mixture toxicity is essential to enable re-use of the data and facilitate nanoinformatics approaches for design of safer nanomaterials for water quality monitoring and remediation technologies. Hence, all data from this work were annotated and integrated into the NanoCommons Knowledge Base, connecting the experimental data to nanoinformatics platforms under the FAIR data principles and making them interoperable with similar datasets.

Interaction of graphene oxide with cell culture medium: Evaluating the fetal bovine serum protein corona formation towards in vitro nanotoxicity assessment and nanobiointeractions.

The interaction of single-layer graphene oxide (SLGO) and multi-layered graphene oxide (MLGO) with a cell culture medium (i.e. DMEM) was studied by evaluating fetal bovine serum (FBS) protein corona formation towards in vitro nanotoxicity assessment and nanobiointeractions. SLGO and MLGO exhibited different colloidal behavior in the culture medium, which was visualized by cryogenic transmission electron microscopy in situ analysis. Exploring proteomics and bioinformatics tools, 394 and 290 proteins were identified on the SLGO and MLGO hard corona compositions, respectively. From this amount, 115 proteins were exclusively detected on the SLGO and merely 11 on MLGO. SLGO enriched FBS proteins involved in metabolic processes and signal transduction, while MLGO enriched proteins involved in cellular development/structure, and lipid transport/metabolic processes. Such a distinct corona profile is due to differences on surface chemistry, aggregation behavior and the surface area of GO materials. Hydrophilic interactions were found to play a greater role in protein adsorption by MLGO than SLGO. Our results point out implications for in vitro studies of graphene oxide materials concerning the effective dose delivered to cells and corona bioactivity. Finally, we demonstrated the importance of integrating conventional and modern techniques thoroughly to understand the GO-FBS complexes towards more precise, reliable and advanced in vitro nanotoxicity assessment.

Co-exposure of graphene oxide with trace elements: Effects on acute ecotoxicity and routine metabolism in Palaemon pandaliformis (shrimp).

Graphene oxide (GO) has been evaluated for application in environmental remediation and pollution control strategies. However, the side effects caused by the interactions of GO with classical pollutants in aquatic environments are still largely unknown. In this work, the ecotoxicological effects of GO, cadmium, zinc and the interactions between GO and these trace elements (co-exposure) were evaluated through acute toxicity tests and routine metabolism (i.e., oxygen consumption and ammonia excretion) in Palaemon pandaliformis (shrimp). After 96 h of exposure, GO did not present acute ecotoxicity at concentrations up to 5.0 mg L-1. However, the association of GO with Cd or Zn increased the toxicity of these trace elements as demonstrated by the decrease in LC50 values. The 96 h LC50 of Cd associated with GO was 1.7 times less than the 96 h LC50 of Cd alone. Similarly, the 96 h LC50 of Zn associated with GO was 1.8 times less than the 96 h LC50 of Zn alone. Additionally, the co-exposure of GO with trace elements impaired the routine metabolism of P. pandaliformis. Finally, the GO potentiated the ecotoxicological effects of Cd and Zn in the shrimp model. Future research on this emerging nanomaterial should focus on its use and disposal in aquatic ecosystems.

Biological effects of oxidized carbon nanomaterials (1D versus 2D) on Spodoptera frugiperda: Material dimensionality influences on the insect development, performance and nutritional physiology.

In this work, we developed an integrative experimental design to investigate the long-term effects of two important classes of carbon nanomaterials with different dimensionalities (i.e., 1D oxidized multiwalled carbon nanotube, ox-MWCNT, and 2D graphene oxide, GO) on the development of the generalist insect Spodoptera frugiperda (Lepidoptera: Noctuidae). Insects are exciting in vivo biological models for investigating the impact of nanomaterials on nanobio-ecological interactions. S. frugiperda larvae were reared from egg hatching to pupation on diets containing ox-MWCNT and GO at different concentrations (0, 10, 100 and 1000 µg g-1 of dry mass of diet). Several aspects of larval and adult performance were measured under controlled conditions. The effects of the carbon nanomaterial (CNM)-containing diets on the nutritional physiology and digestive enzymatic activities of S. frugiperda larvae were also evaluated. The results showed that the type and concentration of CNMs in the diet negatively affected the reproductive parameters and the digestive and metabolic efficiency of S. frugiperda. The diet containing the highest concentration of GO significantly reduced the fecundity and fertility of S. frugiperda compared to the effects of other treatments. S. frugiperda larvae showed decreased efficiency of food conversion into biomass and maximal approximate digestibility when fed diets containing GO at higher concentrations. However, quantitative differences in digestive enzyme activities were not observed between all treatments. These findings highlighted the critical influence of CNM dimensionality on the general performance and nutritional physiology of the moth. This work contributes to the safety evaluation and future applications of CNMs in agri-environmental nanotechnology.

Toxicity assessment of TiO2-MWCNT nanohybrid material with enhanced photocatalytic activity on Danio rerio (Zebrafish) embryos.

The increasing production and use of nanomaterials is causing serious concerns about their safety to human and environmental health. However, the applications of titanium dioxide nanoparticles (TiO2NP) and multiwalled carbon nanotubes (MWCNT) hybrids has grown considerably, due to their enhanced photocatalytic efficiency. To our knowledge, there are no reports available to the scientific community about their toxicity. In this work, we perform a toxicity assessment of TiO2NP and TiO2-MWCNT nanohybrid materials using Zebrafish embryos standardized 96 h early life stage assay, under different exposure conditions (with and without UV light exposure). After exposure the parameters assessed were acute toxicity, hatching rate, growth, yolk sac size, and sarcomere length. In addition, µ-probe X-ray fluorescence spectroscopy (µ-XRF) was employed to observe if nanoparticles were uptaken by zebrafish embryos and consequently accumulated in their organisms. Neither TiO2NP nor TiO2-MWCNT nanohybrids presented acute toxicity to the zebrafish embryos. Moreover, TiO2NP presents sublethal effects for total length (with and without UV light exposure) on the embryos. This work contributes to the understanding of the potential adverse effects of the emerging nanohybrid materials towards safe innovation approaches in nanotechnology.

Interactions of oxidized multiwalled carbon nanotube with cadmium on zebrafish cell line: The influence of two co-exposure protocols on in vitro toxicity tests.

The widespread production and application of carbon nanotubes (CNT) have raising concerns about their release into the environment and, the joint toxicity of CNT with pre-existing contaminants needs to be assessed. This is the first study that investigated the co-exposure of oxidized multiwalled carbon nanotubes (ox-MWCNT) and cadmium (Cd) using a zebrafish liver cell line (ZFL). Two in vitro co-exposure protocols differing by the order of ox-MWCNT interaction with Cd and fetal bovine serum (FBS) proteins were evaluated. Ox-MWCNT was physical and chemical characterized and its adsorption capacity and colloidal stability in cell culture medium was determined in both protocols. Cytotoxicity was investigated by MTT, neutral red, trypan blue, lactate dehydrogenase assays and the necrosis and apoptosis events were determined using flow cytometer. The Cd presence in medium did not interfere in the protein corona composition of MWCNT but the order of interaction of FBS and Cd interfered in its colloidal stability and metal adsorption rate. The ox-MWCNT increased Cd toxicity at low concentration probably by a "Trojan horse" and/or synergistic effect, and induced apoptosis and necrosis in ZFL cells. Although it was not observed differences of toxicity between protocols, the interaction of ox-MWCNT first with Cd led to its precipitation in cell culture medium and, as a consequence, to a possible false viability result by neutral red assay. Taken together, it was evident that the order of compounds interactions disturbs the colloidal stability and affects the in vitro toxicological assays. Considering that Protocol A showed more ox-MWCNT stability after interaction with Cd, this protocol is recommended to be adopted in future studies.

Nanoecotoxicity assessment of graphene oxide and its relationship with humic acid.

The risk assessment of nanomaterials is essential for regulatory purposes and for sustainable nanotechnological development. Although the application of graphene oxide has been widely exploited, its environmental risk is not well understood because several environmental conditions can affect its behavior and toxicity. In the present study, the graphene oxide effect from aquatic ecosystems was assessed considering the interaction with humic acid on 9 organisms: Raphidocelis subcapitata (green algae), Lemna minor (aquatic plant), Lactuca sativa (lettuce), Daphnia magna (planktonic microcrustacean), Artemia salina (brine shrimp), Chironomus sancticaroli (Chironomidae), Hydra attenuata (freshwater polyp), and Caenorhabditis elegans and Panagrolaimus sp. (nematodes). The no-observed-effect concentration (NOEC) was calculated for each organism. The different criteria used to calculate NOEC values were transformed and plotted as a log-logistic function. The hypothetical 5 to 50% hazardous concentration values were, respectively, 0.023 (0.005-0.056) and 0.10 (0.031-0.31) mg L-1 for graphene oxide with and without humic acid, respectively. The safest scenario associated with the predicted no-effect concentration values for graphene oxide in the aquatic compartment were estimated as 20 to 100 µg L-1 (in the absence of humic acid) and 5 to 23 µg L-1 (in the presence of humic acid). Finally, the present approach contributed to the risk assessment of graphene oxide-based nanomaterials and the establishment of nano-regulations. Environ Toxicol Chem 2018;37:1998-2012. © 2018 SETAC.

Covalent functionalization of graphene oxide with d-mannose: evaluating the hemolytic effect and protein corona formation.

In this work, graphene oxide (GO) was covalently functionalized with d-mannose (man-GO) using mannosylated ethylenediamine. XPS (C1s and N1s) confirmed the functionalization of GO through the binding energies at 288.2 eV and 399.8 eV, respectively, which are attributed to the amide bond. ATR-FTIR spectroscopy showed an increase in the amine bond intensity, at 1625 cm-1 (stretching C[double bond, length as m-dash]O), after the functionalization step. Furthermore, the man-GO toxicity to human red blood cells (hemolysis) and its nanobiointeractions with human plasma proteins (hard corona formation) were evaluated. The mannosylation of GO drastically reduced its toxicity to red blood cells. SDS-PAGE analysis showed that the mannosylation process of GO also drastically reduced the amount of the proteins in the hard corona. Additionally, proteomics analysis by LC-MS/MS revealed 109 proteins in the composition of the man-GO hard corona. Finally, this work contributes to future biomedical applications of graphene-based materials functionalized with active biomolecules.

Coating carbon nanotubes with humic acid using an eco-friendly mechanochemical method: Application for Cu(II) ions removal from water and aquatic ecotoxicity.

In this work, industrial grade multi-walled carbon nanotubes (MWCNT) were coated with humic acid (HA) for the first time by means of a milling process, which can be considered an eco-friendly mechanochemical method to prepare materials and composites. The HA-MWCNT hybrid material was characterized by atomic force microscopy (AFM), scanning electron microscopies (SEM and STEM), X-ray photoelectron spectroscopy (XPS), termogravimetric analysis (TGA), and Raman spectroscopy. STEM and AFM images demonstrated that the MWCNTs were efficiently coated by the humic acid, thus leading to an increase of 20% in the oxygen content at the nanotube surface as observed by the XPS data. After the milling process, the carbon nanotubes were shortened as unveiled by SEM images and the values of ID/IG intensity ratio increased due to shortening of the nanotubes and increasing in the number defects at the graphitic structure of carbon nanotubes walls. The analysis of TGA data showed that the quantity of the organic matter of HA on the nanotube surface was 25%. The HA coating was responsible to favor the dispersion of MWCNTs in ultrapure water (i.e. -42mV, zeta-potential value) and to improve their capacity for copper removal. HA-MWCNTs hybrid material adsorbed 2.5 times more Cu(II) ions than oxidized MWCNTs with HNO3, thus evidencing that it is a very efficient adsorbent material for removing copper ions from reconstituted water. The HA-MWCNTs hybrid material did not show acute ecotoxicity to the tested aquatic model organisms (Hydra attenuata, Daphnia magna, and Danio rerio embryos) up to the highest concentration evaluated (10mgL-1). The results allowed concluding that the mechanochemical method is effective to coat carbon nanotubes with humic acid, thus generating a functional hybrid material with low aquatic toxicity and great potential to be applied in environmental nanotechnologies such as the removal of heavy metal ions from water.

Nanotoxicity of graphene oxide: Assessing the influence of oxidation debris in the presence of humic acid.

This study sought to evaluate the toxicological effects of graphene oxide (GO) through tests with Danio rerio (zebrafish) embryos, considering the influence of the base washing treatment and the interaction with natural organic matter (i.e., humic acid, HA). A commercial sample of GO was refluxed with NaOH to remove oxidation debris (OD) byproducts, which resulted in a base washed GO sample (bw-GO). This process decreased the total oxygenated groups in bw-GO and its stability in water compared to GO. When tested in the presence of HA, both GO and bw-GO stabilities were enhanced in water. Although the embryo exposure showed no acute toxicity or malformation, the larvae exposed to GO showed a reduction in their overall length and acetylcholinesterase activity. In the presence of HA, GO also inhibited acid phosphatase activity. Our findings indicate a mitigation of material toxicity after OD removal. The difference in the biological effects may be related to the materials' bioavailability and biophysicochemical interactions. This study reports for the first time the critical influence of OD on the GO material biological reactivity and HA interaction, providing new data for nanomaterial environmental risk assessment and sustainable nanotechnology.

Activated carbon from pyrolysed sugarcane bagasse: Silver nanoparticle modification and ecotoxicity assessment.

Activated carbon from pyrolysed sugarcane bagasse (ACPB) presented pore size ranges from 1.0 to 3.5nm, and surface area between 1200 and 1400m(2)g(-1) that is higher than commonly observed to commercial activated carbon. The ACPB material was successfully loaded with of silver nanoparticles with diameter around 35nm (0.81wt.%). X-ray photoelectron spectroscopy (XPS) analyses showed that the material surface contains metallic/Ag(0) (93.60wt.%) and ionic/Ag(+) states (6.40wt.%). The adsorption capacity of organic model molecules (i.e. methylene blue and phenol) was very efficient to ACPB and ACPB loaded with silver nanoparticles (ACPB-AgNP), indicating that the material modification with silver nanoparticles has not altered its adsorption capacity. ACPB-AgNP inhibited bacteria growth (Escherichia coli), it is a promising advantage for the use of these materials in wastewater treatment and water purification processes. However, ACPB-AgNP showed environmental risks, with toxic effect to the aquatic organism Hydra attenuata (i.e. LC50 value of 1.94mgL(-1)), and it suppressed root development of Lycopersicum esculentum plant (tomato). Finally, this work draw attention for the environmental implications of activated carbon materials modified with silver nanoparticles.

Silver nanoparticle protein corona and toxicity: a mini-review.

Silver nanoparticles are one of the most important materials in the nanotechnology industry. Additionally, the protein corona is emerging as a key entity at the nanobiointerface; thus, a comprehensive understanding of the interactions between proteins and silver nanoparticles is imperative. Therefore, literature reporting studies involving both single molecule protein coronas (i.e., bovine and human serum albumin, tubulin, ubiquitin and hyaluronic-binding protein) and complex protein coronas (i.e., fetal bovine serum and yeast extract proteins) were selected to demonstrate the effects of protein coronas on silver nanoparticle cytotoxicity and antimicrobial activity. There is evidence that distinct and differential protein components may yield a "protein corona signature" that is related to the size and/or surface curvature of the silver nanoparticles. Therefore, the formation of silver nanoparticle protein coronas together with the biological response to these coronas (i.e., oxidative stress, inflammation and cytotoxicity) as well as other cellular biophysicochemical mechanisms (i.e., endocytosis, biotransformation and biodistribution) will be important for nanomedicine and nanotoxicology. Researchers may benefit from the information contained herein to improve biotechnological applications of silver nanoparticles and to address related safety concerns. In summary, the main aim of this mini-review is to highlight the relationship between the formation of silver nanoparticle protein coronas and toxicity.