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In the nanosafety projects funded by the European Commission a large amount of data has been generated on hazard and exposure for a variety of engineered nanomaterials (ENMs) and nano-enabled products (NEPs). However, not all the data generated has been published, nor has all the data been stored in an organised manner (e. g. database) which makes it very difficult for researchers, industry and other stakeholders to use it. This paper provides an inventory of NEPs studied in each of these projects, including relevant information on the NEPs, the life-cycle stages evaluated for each of them and an overview of the projects, which can be used for identifying areas in which there might be data gaps. The purpose of analyzing the nanosafety research done on NEPs was to provide an overview of the products studied compare to what can realistically be found in the market (i.e. the exposure relevant materials that workers, consumers and the environment may be exposed to). The analysis done in all the projects included in the inventory allowed the identification of the need to increase the number of studies with well-established commercialized NEPs, such as ENMs used in tyres or sunscreens. In addition, it was found that, in general, there was a correlation of the different ENMs studied with their respective production relevance (i.e. production volumes), except for silver, which was vastly over-represented, and on the other hand carbon black, which was under-represented. Addittionally, there is a need to improve accessibility to relevant and high quality data produced in all these projects to provide transparency and support to different stakeholder needs.

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Nanotechnology is identified as a key enabling technology due to its potential to contribute to economic growth and societal well-being across industrial sectors. Sustainable nanotechnology requires a scientifically based and proportionate risk governance structure to support innovation, including a robust framework for environmental risk assessment (ERA) that ideally builds on methods established for conventional chemicals to ensure alignment and avoid duplication. Exposure assessment developed as a tiered approach is equally beneficial to nano-specific ERA as for other classes of chemicals. Here we present the developing knowledge, practical considerations and key principles need to support exposure assessment for engineered nanomaterials for regulatory and research applications.

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Engineered nanoparticles (NPs) entering the environment are subject to various transformations that in turn influence how particles are presented to, and taken up by, organisms. To understand the effect of soil properties on the toxicity of nanosilver to Caenorhabditis elegans, toxicity assays were performed in porewater extracts from natural soils with varying organic matter content and pH using 3-8 nm unfunctionalized silver (Ag 3-8Unf), 52-nm polyvinylpyrrolidone (PVP)-coated Ag NPs (Ag 52PVP), and AgNO3 as ionic Ag. Effects on NP agglomeration and stability were investigated using ultraviolet-visible (UV-vis) spectroscopy and asymmetric flow field-flow fractionation (AF4); Ag+ showed greater overall toxicity than nanosilver, with little difference between the NP types. Increasing soil organic matter content significantly decreased the toxicity of Ag 3-8Unf, whereas it increased that of AgNO3 . The toxicity of all Ag treatments significantly decreased with increasing porewater pH. Dissolution of both NPs in the porewater extracts was too low to have contributed to their observed toxic effects. The UV-vis spectroscopy revealed low levels of agglomeration/aggregation independent of soil properties for Ag 3-8Unf, whereas higher organic matter as well as low pH appeared to stabilize Ag 52PVP. Overall, both soil organic matter content and pH affected NP fate as well as toxicity to C. elegans; however, there appears to be no clear connection between the measured particle characteristics and their effect. Environ Toxicol Chem 2018;37:2609-2618. © 2018 SETAC.

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Silver nanoparticles (AgNPs) are widely used worldwide, most likely leading to their release into the environment and a subsequent increase of environmental concentrations. Studies of their deleterious effects on organisms is crucial to understand their environmental impacts. The freshwater snail Physa acuta was chosen to evaluate the potential deleterious effects of AgNPs and their counterpart AgNO3 , through water-only exposures. The toxicity of AgNPs is greatly influenced by medium composition. Thus, 2 media were tested: artificial pond water (APW) and modified APW (adapted by removing calcium chloride). Acute tests (96 h) were performed with juvenile and adult snails in both media to assess lethality, and egg mass chronic tests were conducted with APW medium only to assess embryo viability and mortality, carried out until 90% hatching success was reached in the control. Acute toxicity increased with decreasing shell length for both silver forms (ion and nanoparticle); that is, juveniles were more sensitive than adults. Different test media led to dissimilar median lethal concentrations, with chloride playing an important role in toxicity, most likely by complexation with silver ions, which would reduce the bioavailability, uptake, and toxicity of silver. Chronic tests showed that hatching success was more sensitive to silver in the ionic form than in the particulate form. Different forms of silver, exposure media, and life cycle stages led to different patterns of toxicity, highlighting an impairment in the snails' life cycle. Environ Toxicol Chem 2017;36:243-253. © 2016 SETAC.

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We herein report the synthesis of novel "Janus" calix[4]arenes bearing four "molecular tethering" functional groups on either the upper or lower rims of the calixarene. These enable facile multipoint covalent attachment to electrode surfaces with monolayer coverage. The other rim of the calixarenes bear either four azide or four ethynyl functional groups, which are easily modified by the copper(I)-catalyzed azide-alkyne cycloaddition reaction (CuAAC), either pre- or postsurface modification, enabling these conical, nanocavity reactor sites to be decorated with a wide range of substrates to impart desired chemical properties. Redox active species decorating the peripheral rim are shown to be electrically connected by the calixarene to the electrode surface in either "up" or "down" orientations of the calixarene.

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The effects from multigenerational exposures to engineered nanoparticles (ENPs) in their pristine and transformed states are currently unknown despite such exposures being an increasingly common scenario in natural environments. Here, we examine how exposure over 10 generations affects the sensitivity of the nematode Caenorhabditis elegans to pristine and sulfidized Ag ENPs and AgNO3 We also include populations that were initially exposed over six generations but kept unexposed for subsequent four generations to allow recovery from exposure. Toxicity of the different silver forms decreased in the order AgNO3, Ag ENPs and Ag2S ENPs. Continuous exposure to Ag ENPs and AgNO3 caused pronounced sensitization (approx. 10-fold) in the F2 generation, which was sustained until F10. This sensitization was less pronounced for Ag2S ENP exposures, indicating different toxicity mechanisms. Subtle changes in size and lifespan were also measured. In the recovery populations, the sensitivity to Ag ENPs and AgNO3 resulting from the initial multigenerational exposure persisted. Their response sensitivity for all endpoints was most closely related to the last ancestral exposed generation (F5), rather than unexposed controls. The mechanisms of transgenerational transfer of sensitivity are probably organized through the epigenome, and we encourage others to investigate such effects as a priority for mechanistic toxicology.

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Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120 µm min(-1)) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials.

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Initiatives to support the sustainable development of the nanotechnology sector have led to rapid growth in research on the environmental fate, hazards and risk of engineered nanoparticles (ENP). As the field has matured over the last 10 years, a detailed picture of the best methods to track potential forms of exposure, their uptake routes and best methods to identify and track internal fate and distributions following assimilation into organisms has begun to emerge. Here we summarise the current state of the field, focussing particularly on metal and metal oxide ENPs. Studies to date have shown that ENPs undergo a range of physical and chemical transformations in the environment to the extent that exposures to pristine well dispersed materials will occur only rarely in nature. Methods to track assimilation and internal distributions must, therefore, be capable of detecting these modified forms. The uptake mechanisms involved in ENP assimilation may include a range of trans-cellular trafficking and distribution pathways, which can be followed by passage to intracellular compartments. To trace toxicokinetics and distributions, analytical and imaging approaches are available to determine rates, states and forms. When used hierarchically, these tools can map ENP distributions to specific target organs, cell types and organelles, such as endosomes, caveolae and lysosomes and assess speciation states. The first decade of ENP ecotoxicology research, thus, points to an emerging paradigm where exposure is to transformed materials transported into tissues and cells via passive and active pathways within which they can be assimilated and therein identified using a tiered analytical and imaging approach.

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Filamentous hyphae of the human pathogen, Candida albicans, invade mucosal layers and medical silicones. In vitro, hyphal tips reorient thigmotropically on contact with small obstacles. It is not known how surface topography is sensed but hyphae lacking the cortical marker, Rsr1/Bud1, are unresponsive. We show that, on surfaces, the morphology of hyphal tips and the position of internal polarity protein complexes are asymmetrically skewed towards the substratum and biased towards the softer of two surfaces. In nano-fabricated chambers, the Spitzenkörper (Spk) responded to touch by translocating across the apex towards the point of contact, where its stable maintenance correlated with contour-following growth. In the rsr1Δ mutant, the position of the Spk meandered and these responses were attenuated. Perpendicular collision caused lateral Spk oscillation within the tip until after establishment of a new growth axis, suggesting Spk position does not predict the direction of growth in C. albicans. Acute tip reorientation occurred only in cells where forward growth was countered by hyphal friction sufficient to generate a tip force of ∼ 8.7 µN (1.2 MPa), more than that required to penetrate host cell membranes. These findings suggest mechanisms through which the organization of hyphal tip growth in C. albicans facilitates the probing, penetration and invasion of host tissue.

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In this work it has been established that 3D nanoflowers of WS2 synthesised by chemical vapour deposition are composed of few layer WS2 along the edges of the petals. An experimental study in order to understand the evolution of these nanostructures shows the nucleation and growth along with the compositional changes they undergo.

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To progress from the laboratory to commercial applications, it will be necessary to develop industrially scalable methods to produce large quantities of defect-free graphene. Here we show that high-shear mixing of graphite in suitable stabilizing liquids results in large-scale exfoliation to give dispersions of graphene nanosheets. X-ray photoelectron spectroscopy and Raman spectroscopy show the exfoliated flakes to be unoxidized and free of basal-plane defects. We have developed a simple model that shows exfoliation to occur once the local shear rate exceeds 10(4) s(-1). By fully characterizing the scaling behaviour of the graphene production rate, we show that exfoliation can be achieved in liquid volumes from hundreds of millilitres up to hundreds of litres and beyond. The graphene produced by this method performs well in applications from composites to conductive coatings. This method can be applied to exfoliate BN, MoS2 and a range of other layered crystals.

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Silver nanoparticles (AgNP) have gained attention over the years due to the antimicrobial function of silver, which has been exploited industrially to produce consumer goods that vary in type and application. Undoubtedly the increase of production and consumption of these silver-containing products will lead to the entry of silver compounds into the environment. In this study we have used Pseudokirchneriella subcapitata, Daphnia magna and Danio rerio as model organisms to investigate the toxicity of AgNP and AgNO3 by assessing different biological endpoints and exposure periods. Organisms were exposed following specific and standardized protocols for each species/endpoints, with modifications when necessary. AgNP were characterized in each test-media by Transmission Electron Microscopy (TEM) and experiments were performed by Dynamic Light Scattering (DLS) to investigate the aggregation and agglomeration behavior of AgNP under different media chemical composition and test-period. TEM images of AgNP in the different test-media showed dissimilar patterns of agglomeration, with some agglomerates inside an organic layer, some loosely associated particles and also the presence of some individual particles. The toxicity of both AgNO3 and AgNP differ significantly based on the test species: we found no differences in toxicity for algae, a small difference for zebrafish and a major difference in toxicity for Daphnia magna.

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As the production of zinc oxide nanoparticles (ZnO-NPs) and other metal oxides is exponentially increasing, it is important to investigate potential environmental and health impacts of such nanoparticles. Nanoparticles' properties (e.g., size, dissolution rate) may change in different water media, and their characterization is essential to derive conclusions about toxicity results. Therefore, an aquatic model organism, Daphnia magna, was used to investigate the effect of ZnO-NPs with 2 different particle sizes (30 nm and 80-100 nm) and then compare these effects with ZnO microsized particles (>200 nm) and the ionic counterpart (in the form of ZnCl2 ) on immobilization, feeding inhibition, and reproduction endpoints. The 48-h median lethal concentration (LC50) for immobilization ranged between 0.76 mg Zn L(-1) for the ionic zinc and 1.32 mg Zn L(-1) for ZnO-NPs of 80 nm to 100 nm. For the chronic exposures, the reproduction output was impaired similarly among zinc exposures and possibly driven mainly by the zinc ionic form. The concentrations used showed a total dissolution after 48 h. On the other hand, feeding activity was more affected by the 30 nm ZnO-NPs than by the ionic zinc, showing that the particulate form was also playing an important role in the feeding inhibition of D. magna. Dissolution and particle size in the daphnia test media were found to be essential to derive conclusions on toxicity. Therefore, they can possibly be considered critical for evaluating nanoparticles' toxicity and fate.

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Electrodeposition methods are used to generate a sparse array of platinum nanoparticles on a glassy carbon electrode. Specifically electrodeposition from a 1 mM solution of H2PtCl6 in 0.5 M H2SO4 leads to surface coverages of 0.46% to 1.96% and nanoparticles of size 29 nm to 136 nm in diameter, using deposition times of 30 and 15 seconds. The reduction of oxygen at an array of 29 nm nanoparticles with a surface coverage of 0.46% showed voltammetric signals with a scan rate dependence consistent with a two electron reduction of O2 to H2O2 with the rate proportional to K0 exp(-α(E-Ef(0))/RT) and formal potential (Ef(0)) of -0.058 V vs. SHE, a standard electrochemical rate constant (k0) of ~10 cm s(-1) and a transfer coefficient (α) of 0.23. At higher Pt nanoparticle coverages, a scan rate dependence consistent with the partial further reduction of H2O2 to water becomes evident.

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Analytical expressions for the anodic stripping voltammetry of metallic nanoparticles from an electrode are provided. First, for reversible electron transfer, two limits are studied: that of diffusionally independent nanoparticles and the regime where the diffusion layers originating from each particle overlap strongly. Second, an analytical expression for the voltammetric response under conditions of irreversible electron transfer kinetics is also derived. These equations demonstrate how the peak potential for the stripping process is expected to occur at values negative of the formal potential for the redox process in which the surface immobilised nanoparticles are oxidised to the corresponding metal cation in the solution phase. This work is further developed by considering the surface energies of the nanoparticles and its effect on the formal potential for the oxidation. The change in the formal potential is modelled in accordance with the equations provided by Plieth [J. Phys. Chem., 1982, 86, 3166-3170]. The new analytical expressions are used to investigate the stripping of silver nanoparticles from a glassy carbon electrode. The relative invariance of the stripping peak potential at low surface coverages of silver is shown to be directly related to the surface agglomeration of the nanoparticles.

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Consecutive electro-oxidation and reduction cycling of gold macroelectrodes in sulphuric acid medium is a widely-used cleaning and calibration procedure. In this paper this method is applied to electrodeposited nanoparticles revealing significant differences in the electro-oxidation process and the cleaning effectiveness. This suggests a higher density of surface defects on the nanoparticles.

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Anodic particle coloumetry is used to size silver nanoparticles impacting a carbon microelectrode in a potassium chloride/citrate solution. Besides their size, their agglomeration state in solution is also investigated solely by electrochemical means and subsequent data analysis. Validation of this new approach to nanoparticle agglomeration studies is performed by comparison with the results of a commercially available nanoparticle tracking analysis system, which shows excellent agreement. Moreover, it is demonstrated that the electrochemical technique has the advantage of directly yielding the number of atoms per impacting nanoparticle irrespective of its shape. This is not true for the optical nanoparticle tracking system, which requires a correction for the nonspherical shape of agglomerated nanoparticles to derive reasonable information on the agglomeration state.

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Nanographene oxide (NGO) is a novel nano-wall material that tracks to tumors in vivo, and which, as a consequence of its large surface area, has the capacity to carry a large payload. This study explores the use of anti-HER2 antibody (trastuzumab)-conjugated NGO, radiolabeled with (111)In-benzyl-diethylenetriaminepentaacetic acid (BnDTPA) via ππ-stacking, for functional imaging. In two HER2-overexpressing murine models of human breast cancer, high tumor-to-muscle ratio was achieved, resulting in clear visualization of tumor using single-photon emission computed tomography (SPECT). In the BALB/neuT model and in BALB/c nu/nu mice bearing 231/H2N xenografts, tumor accumulation amounted to 12.7 ± 0.67 and 15.0 ± 3.7% of the injected dose/g (%ID/g) of tumor tissue at 72 h, with tumor-to-muscle ratios of 35:1 and 7:1, respectively. Radiolabeled NGO-trastuzumab conjugates demonstrated superior pharmacokinetics compared to radiolabeled trastuzumab without NGO, with more rapid clearance from the circulation. The use of NGO as a scaffold to build radiolabeled nano-immunoconstructs holds promise for molecular imaging of tumors.

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The investigation of electrocatalytic nanoeffects is tackled via joint electrochemical measurements and computational simulations. The cyclic voltammetry of electrodes modified with metal nanoparticles is modeled considering the kinetics of the electrochemical process on the bulk materials of the different regions of the electrode, that is, the substrate (glassy carbon) and the nanoparticles (gold). Comparison of experimental and theoretical results enables the detection of changes in the electrode kinetics at the nanoscale due to structural and/or electronic effects. This approach is applied to the experimental assessment of electrocatalytic effects by gold nanoparticles (Au NPs) in the electrooxidation of nitrite and L-ascorbate. Glassy carbon electrode is modified with Au NPs via seed-mediated growth method. Divergence between the kinetics of these processes on gold macroelectrodes and gold nanoparticles is examined. Whereas claimed catalytic effects are not observed in the electrooxidation of nitrite, electrocatalytic nanoeffects are verified in the case of L-ascorbate. This is probably due to that the electron transfer process follows an adsorptive mechanism. The combination of simulation with experiments is commended as a general strategy of authentification, or not, of nanoelectrocatalytic effects.

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A fast and cheap in situ approach is presented for the characterization of gold nanoparticles from electrochemical experiments. The average size and number of nanoparticles deposited on a glassy carbon electrode are determined from the values of the total surface area and amount of gold obtained by lead underpotential deposition and by stripping of gold in hydrochloric acid solution, respectively. The morphology of the nanoparticle surface can also be analyzed from the "fingerprint" in lead deposition/stripping experiments. The method is tested through the study of gold nanoparticles deposited on a glassy carbon substrate by seed-mediated growth method which enables an easy control of the nanoparticle size. The procedure is also applied to the characterization of supplied gold nanoparticles. The results are in satisfactory agreement with those obtained via scanning electron microscopy.

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