We have studied the occurrence of phase transitions in two polymorphs of BiVO4 under high-pressure and high-temperature conditions by means of X-ray diffraction measurements. The fergusonite ...polymorph undergoes a phase transition at 1.5(1) GPa and room temperature into a tetragonal scheelite-type structure. The same transition takes place at 523(1) K and ambient pressure. A second phase transition takes place at room temperature under compression at 16(1) GPa. The transition is from the tetragonal scheelite structure to a monoclinic structure (space group P21/c). All observed phase transitions are reversible. The zircon polymorph counterpart also transforms under compression into the scheelite-type structure. In this case, the transitions take place at 4.3(1) GPa and room temperature and at 653(1) K and ambient pressure. The zircon–scheelite transition is nonreversible. The experiments support that the fergusonite–scheelite transformation is a second-order transition and that the zircon–scheelite transformation is a first-order transition. Finally, we have also determined the compressibility and the thermal expansion of the fergusonite, scheelite, and zircon phases.
The NanoRelease Food Additive project developed a catalog to identify potential engineered nanomaterials (ENMs) used as ingredients, using various food‐related databases. To avoid ongoing debate on ...defining the term nanomaterial, NanoRelease did not use any specific definition other than the ingredient is not naturally part of the food chain, and its dimensions are measured in the nanoscale. Potential nanomaterials were categorized based on physical similarity; analysis indicated that the range of ENMs declared as being in the food chain was limited. Much of the catalog's information was obtained from product labeling, likely resulting in both underreporting (inconsistent or absent requirements for labeling) and/or overreporting (inability to validate entries, or the term nano was used, although no ENM material was present). Three categories of ingredients were identified: emulsions, dispersions, and their water‐soluble powdered preparations (including lipid‐based structures); solid encapsulates (solid structures containing an active material); and metallic or other inorganic particles. Although much is known regarding the physical/chemical properties for these ingredient categories, it is critical to understand whether these properties undergo changes following their interaction with food matrices during preparation and storage. It is also important to determine whether free ENMs are likely to be present within the gastrointestinal tract and whether uptake of ENMs may occur in their nanoform physical state. A practical decision‐making scheme was developed to help manage testing requirements.
The incorporation of small amounts of nanofillers in polymeric matrices has enabled new applications in several industrial sectors. The nanofiller dispersion can be improved by modifying the ...nanomaterial (NM) surface or predispersing the NMs to enhance compatibility. This study evaluates the effect of these compatibilization strategies on migration/release of the nanofiller and transformation of polyamide-6 (PA6), a thermoplastic polymer widely used in industry during simulated outdoors use. Two nanocomposites (NCs) containing SiO2 nanoparticles (NPs) with different surface properties and two multiwalled carbon nanotube (MWCNT) NCs obtained by different addition methods were produced and characterized, before and after accelerated wet aging conditions. Octyl-modified SiO2 NPs, though initially more aggregated than uncoated SiO2 NPs, reduced PA6 hydrolysis and, consequently, NM release. Although no clear differences in dispersion were observed between the two types of MWCNT NCs (masterbatch vs direct addition) after manufacture, the use of the MWCNT masterbatch reduced PA6 degradation during aging, preventing MWCNT accumulation on the surface and further release or potential exposure by direct contact. The amounts of NM released were lower for MWCNTs (36 and 108 mg/m2) than for SiO2 NPs (167 and 730 mg/m2), being lower in those samples where the NC was designed to improve the nanofiller–matrix interaction. Hence, this study shows that optimal compatibilization between NM and matrix can improve NC performance, reducing polymer degradation and exposure and/or release of the nanofiller.
Expect the unexpected: The interaction between cyanuric acid (CA) and melamine (M) molecules is a key structural motif in supramolecular chemistry. The adsorption and coadsorption of M and CA on a ...Au(111) surface under ultrahigh vacuum (UHV) is investigated using STM with submolecular resolution (see image). In addition to the expected structure with a 1:1 CA/M ratio, a novel phase with a 1:3 CA/M forms upon sequential deposition.
Nowadays, hundreds of consumer products contain metal and metal oxide nanoparticles (NP); this increases the probability of such particles to be released to natural waters generating a potential risk ...to human health and the environment. This paper presents the development of efficient carboneous nanofibrous membranes for NP filtration from aqueous solutions. Free-standing carbon nanofiber (CNF) mats with different fiber size distribution ranging from 126 to 554 nm in diameter were produced by electrospinning of polyacrylonitrile (PAN) precursor solution followed by thermal treatment. Moreover, tetraethoxyorthosilicate was added to provide flexibility and increase the specific surface area of the CNF. The resulting membranes are bendable and mechanically strong enough to withstand filtration under pressure or vacuum. The experimental results of filtration revealed that the fabricated membranes could efficiently reject nanoparticles of different types (Au, Ag, and TiO2) and size (from 10 to 100 nm in diameter) from aqueous solutions. It is worth mentioning that the removal of Ag NP with diameters as small as 10 nm was close to 100% with an extremely high flux of 47620 L m−2 h−1 bar−1.
Pulmonary exposure to micro- and nanoscaled particles has been widely linked to adverse health effects and high concentrations of respirable particles are expected to occur within and around many ...industrial settings. In this study, a field-measurement campaign was performed at an industrial manufacturer, during the production of paints. Spatial and personal measurements were conducted and results were used to estimate the mass flows in the facility and the airborne particle release to the outdoor environment. Airborne particle number concentration (1 × 103–1.0 × 104 cm−3), respirable mass (0.06–0.6 mg m−3), and PM10 (0.3–6.5 mg m−3) were measured during pouring activities. In overall; emissions from pouring activities were found to be dominated by coarser particles >300 nm. Even though the raw materials were not identified as nanomaterials by the manufacturers, handling of TiO2 and clays resulted in release of nanometric particles to both workplace air and outdoor environment, which was confirmed by TEM analysis of indoor and stack emission samples. During the measurement period, none of the existing exposure limits in force were exceeded. Particle release to the outdoor environment varied from 6 to 20 g ton−1 at concentrations between 0.6 and 9.7 mg m−3 of total suspended dust depending on the powder. The estimated release of TiO2 to outdoors was 0.9 kg per year. Particle release to the environment is not expected to cause any major impact due to atmospheric dilution
Background The application of nanomaterials (NMs) and nano-enabled products (NEPs) across many industries has been extensive and is still expanding decades after first being identified as an emerging ...technology. Additive manufacturing has been greatly impacted and has seen the benefits of integrating NMs within products. With the expansion of nanotechnology, there has been a need to develop more adaptive and responsive methods to ascertain risks and ensure technology is developed safely. The Safe(r)-by-Design (SbD) concept can be used to establish safe parameters and minimise risks during the materials’ lifecycle, including the early stages of the supply chain. Exposure monitoring has advanced in recent years with the creation of standardised protocols for occupational exposure assessment of nano-objects and their aggregates and agglomerates (NOAA). Methods To aid in the development of an online SbD-supporting platform by the EU-funded project SAbyNA, we adopt a Europe Standard for monitoring release of NOAA to identify if a greater release of NOAA is associated with incorporation of NMs within NEPs compared to a polymer matrix alone. Case studies included filaments of polypropylene (PP) with nano-Ag or polycarbonate (PC) with single-walled carbon nanotubes (SWCNTs). NMs were received in masterbatch, and therefore previously modified to align with SbD interventions. Results were collected in line with European Standard recommendations: monitoring particle concentrations using direct reading instruments (DRI), sampling for offline chemical and morphological analysis, and collecting contextual information. Results and discussion Based on the criteria described in the European standard (BS EN 17058), data from both case studies identified that inhalation exposure relating to NM was “unlikely”. Despite this, during the production of the SWCNT-PC filaments, some noteworthy observations were made, including several DRI activity measurements shown to be higher than background levels, and material morphologically similar to the reference SWCNT/polymeric masterbatch observed in offline analysis. The data collected during this campaign were used to discuss choices available for data interpretation and decision-making in the European Standard for monitoring release of NOAA and also to facilitate the development of SAbyNA’s user-friendly industry platform for the SbD of NMs and NEPs.
Introduction:
Significant progress has been made in terms of best practice in research data management for nanosafety. Some of the underlying approaches to date are, however, overly focussed on the ...needs of specific research projects or aligned to a single data repository, and this “silo” approach is hampering their general adoption by the broader research community and individual labs.
Methods:
State-of-the-art data/knowledge collection, curation management FAIrification, and sharing solutions applied in the nanosafety field are reviewed focusing on unique features, which should be generalised and integrated into a functional FAIRification ecosystem that addresses the needs of both data generators and data (re)users.
Results:
The development of data capture templates has focussed on standardised single-endpoint Test Guidelines, which does not reflect the complexity of real laboratory processes, where multiple assays are interlinked into an overall study, and where non-standardised assays are developed to address novel research questions and probe mechanistic processes to generate the basis for read-across from one nanomaterial to another. By focussing on the needs of data providers and data users, we identify how existing tools and approaches can be re-framed to enable “on-the-fly” (meta) data definition, data capture, curation and FAIRification, that are sufficiently flexible to address the complexity in nanosafety research, yet harmonised enough to facilitate integration of datasets from different sources generated for different research purposes. By mapping the available tools for nanomaterials safety research (including nanomaterials characterisation, nonstandard (mechanistic-focussed) methods, measurement principles and experimental setup, environmental fate and requirements from new research foci such as safe and sustainable by design), a strategy for integration and bridging between silos is presented. The NanoCommons KnowledgeBase has shown how data from different sources can be integrated into a one-stop shop for searching, browsing and accessing data (without copying), and thus how to break the boundaries between data silos.
Discussion:
The next steps are to generalise the approach by defining a process to build consensus (meta)data standards, develop solutions to make (meta)data more machine actionable (on the fly ontology development) and establish a distributed FAIR data ecosystem maintained by the community beyond specific projects. Since other multidisciplinary domains might also struggle with data silofication, the learnings presented here may be transferrable to facilitate data sharing within other communities and support harmonization of approaches across disciplines to prepare the ground for cross-domain interoperability.
The Safe-by-Design (SbD) concept aims to facilitate the development of safer materials/products, safer production, and safer use and end-of-life by performing timely SbD interventions to reduce ...hazard, exposure, or both. Early hazard screening is a crucial first step in this process. In this review, for the first time, commonly used in vitro assays are evaluated for their suitability for SbD hazard testing of nanomaterials (NMs). The goal of SbD hazard testing is identifying hazard warnings in the early stages of innovation. For this purpose, assays should be simple, cost-effective, predictive, robust, and compatible. For several toxicological endpoints, there are indications that commonly used in vitro assays are able to predict hazard warnings. In addition to the evaluation of assays, this review provides insights into the effects of the choice of cell type, exposure and dispersion protocol, and the (in)accurate determination of dose delivered to cells on predictivity. Furthermore, compatibility of assays with challenging advanced materials and NMs released from nano-enabled products (NEPs) during the lifecycle is assessed, as these aspects are crucial for SbD hazard testing. To conclude, hazard screening of NMs is complex and joint efforts between innovators, scientists, and regulators are needed to further improve SbD hazard testing.
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•A convergent synthesis of 1α,25-dihydroxyergocalciferol side-chain homologated analogs for biological studies was achieved.•The triene system was assembled by the Wittig-Horner ...approach.•The key step is the stereoselective introduction of methyl or phenyl groups at C24 by an anti-SN2′ displacement of the phosphate group with cuprates.
As part of our program on search for vitamin D analogs with selective biological properties, such as low or negligible calcemic action, we describe here an efficient and versatile synthetic approach to derivatives of 1α,25-dihydroxyvitamin D2 with homologated side-chains and substitution at C24 for biological evaluation.
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