In silico assessment of nanoparticle toxicity powered by the Enalos Cloud Platform: Integrating automated machine learning and synthetic data for enhanced nanosafety evaluation.

The rapid advance of nanotechnology has led to the development and widespread application of nanomaterials, raising concerns regarding their potential adverse effects on human health and the environment. Traditional (experimental) methods for assessing the nanoparticles (NPs) safety are time-consuming, expensive, and resource-intensive, and raise ethical concerns due to their reliance on animals. To address these challenges, we propose an in silico workflow that serves as an alternative or complementary approach to conventional hazard and risk assessment strategies, which incorporates state-of-the-art computational methodologies. In this study we present an automated machine learning (autoML) scheme that employs dose-response toxicity data for silver (Ag), titanium dioxide (TiO2), and copper oxide (CuO) NPs. This model is further enriched with atomistic descriptors to capture the NPs' underlying structural properties. To overcome the issue of limited data availability, synthetic data generation techniques are used. These techniques help in broadening the dataset, thus improving the representation of different NP classes. A key aspect of this approach is a novel three-step applicability domain method (which includes the development of a local similarity approach) that enhances user confidence in the results by evaluating the prediction's reliability. We anticipate that this approach will significantly expedite the nanosafety assessment process enabling regulation to keep pace with innovation, and will provide valuable insights for the design and development of safe and sustainable NPs. The ML model developed in this study is made available to the scientific community as an easy-to-use web-service through the Enalos Cloud Platform (www.enaloscloud.novamechanics.com/sabydoma/safenanoscope/), facilitating broader access and collaborative advancements in nanosafety.

ASCOT: A web tool for the digital construction of energy minimized Ag, CuO, TiO2 spherical nanoparticles and calculation of their atomistic descriptors.

ASCOT (an acronym derived from Ag-Silver, Copper Oxide, Titanium Oxide) is a user-friendly web tool for digital construction of electrically neutral, energy-minimized spherical nanoparticles (NPs) of Ag, CuO, and TiO2 (both Anatase and Rutile forms) in vacuum, integrated into the Enalos Cloud Platform (https://www.enaloscloud.novamechanics.com/sabydoma/ascot/). ASCOT calculates critical atomistic descriptors such as average potential energy per atom, average coordination number, common neighbour parameter (used for structural classification in simulations of crystalline phases), and hexatic order parameter (which measures how closely the local environment around a particle resembles perfect hexatic symmetry) for both core (over 4 Å from the surface) and shell (within 4 Å of the surface) regions of the NPs. These atomistic descriptors assist in predicting the most stable NP size based on lowest per atom energy and serve as inputs for developing machine learning models to predict the toxicity of these nanomaterials. ASCOT's automated backend requires minimal user input in order to construct the digital NPs: inputs needed are the material type (Ag, CuO, TiO2-Anatase, TiO2-Rutile), target diameter, a Force-Field from a pre-validated list, and the energy minimization parameters, with the tool providing a set of default values for novice users.

Unlocking the potential of nanoscale sulfur in sustainable agriculture.

The global population is growing rapidly, which poses a significant challenge to food security. Innovation in agricultural technologies is necessary to achieve sustainable development in agriculture and combat food insecurity. Nanotechnology has emerged as a promising tool in agriculture; compared to conventional agricultural chemicals, demonstrated benefits include increased efficiency of delivery and utilization of both nutrients and pesticides, as well as nanoscale-specific stimulation of stress tolerance pathways. Among the many studied nanomaterials, nano-sulfur has demonstrated superior effects at enhancing plant resilience to pathogens and abiotic stresses, as well as improving plant growth and nutritional quality of edible tissues. A number of published studies have investigated the physiological effects (growth promotion, disease resistance) of single or several sulfur and sulfide compounds on crop species. However, there is no systematic analysis of this literature, including the effects and specific mechanisms of various sulfur forms in agricultural applications. In this review, we will discuss the effects of sulfur (including nano-sulfur) on crop species, the underlying mechanisms of action for their transport and transformation in the soil-plant system, and evaluate their suitability in sustainable agricultural development. Additionally, we discuss the current challenges and knowledge gaps for nanoscale sulfur use in agriculture, and describe future research directions to advance our understanding of the sustainable use of this material at the scale of individual fields.

Z-scheme Fe@Fe2O3/BiOBr heterojunction with efficient carrier separation for enhanced heterogeneous photo-Fenton activity of tetracycline degradation: Fe2+ regeneration, mechanism insight and toxicity evaluation.

The recombination of photogenerated carrier leads to inefficient Fe2+ regeneration, which limits the extensive application of heterogeneous photo-Fenton. Here, a novel Fe@Fe2O3/BiOBr catalyst with Z-scheme heterojunction structure is designed, and the establishment of the Z-scheme heterojunction facilitates the separation and transfer of photogenerated carrier and maintains the superior redox capability of the system. As-prepared Fe@Fe2O3/BiOBr catalyst exhibits outstanding catalytic performance and stability, especially for the optimum composite FFB-3, its degradation efficiency of tetracycline (TC) achieves 98.22% and the mineralization degree reaches 59.48% within 90 min under natural pH. The preeminent catalytic efficiency benefited from the synergistic of heterogeneous photo-Fenton and Z-scheme carriers transfer mechanism, where Fe2+ regeneration was achieved by photogenerated electrons, and increased hydroxyl radicals were produced with the participation of H2O2 in-situ generated. The results of free-radical scavenging experiment and ESR illustrated that •OH, •O2-, 1O2 and h+ were active species participating in TC degradation. Furthermore, the TC degradation paths were proposed according to LC-MS, and the toxicity evaluation result showed that the toxicity of TC solutions was markedly decreased after degradation. This study provides an innovative strategy for heterogeneous photo-Fenton degradation of antibiotic contaminations by constructing Z-scheme heterojunctions.

Influence of soil properties and aging on exogenous antimony toxicity to Caenorhabditis elegans in agricultural soil.

Exploring the influence of soil on antimony (Sb) aging could help predict Sb toxicity on nematodes that play an important role in agricultural soil nitrogen cycling. This study aimed to investigate the major soil factors affecting the aging process and toxicity of exogenous Sb. Therefore, nematodes were exposed to varying levels of Sb contamination (0-6400 mg/kg) in nine agricultural soils, with aging periods of 7, 56, and 168 days, under dark conditions at 20 ± 0.5 °C for 96 h. The results suggested that nematode reproduction was more sensitive to the toxicity of exogenous trivalent Sb (Sb(III)) compared to growth and fertility. Following 7-168 days of aging, the EC50 of nematode reproduction increased from 546-1557 to 3560-6193 mg/kg in nine soils contaminated by exogenous Sb(III). Exogenous Sb(III) toxicity is overestimated without considering its aging process. The aging factors (AF) of nine soils aged over 7-168 days were calculated as 3.54-8.03. The regression equation AF = 0.923 pH - 0.812 (n = 9, adjust-r2 = 0.687, P = 0.004) indicated that pH was the primary soil factor explaining 85.2% of the variance in the aging process of exogenous Sb(III). No significant toxicity was observed in soils contaminated with exogenous pentavalent Sb after 7 days of aging. These findings could provide guidance for the adjustment of Sb toxicity data, the revision of soil environmental quality standard, and efficient soil environmental management.

Dynamic Transformation of Nano-MoS2 in a Soil-Plant System Empowers Its Multifunctionality on Soybean Growth.

Molybdenum disulfide (nano-MoS2) nanomaterials have shown great potential for biomedical and catalytic applications due to their unique enzyme-mimicking properties. However, their potential agricultural applications have been largely unexplored. A key factor prior to the application of nano-MoS2 in agriculture is understanding its behavior in a complex soil-plant system, particularly in terms of its transformation. Here, we investigate the distribution and transformation of two types of nano-MoS2 (MoS2 nanoparticles and MoS2 nanosheets) in a soil-soybean system through a combination of synchrotron radiation-based X-ray absorption near-edge spectroscopy (XANES) and single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS). We found that MoS2 nanoparticles (NPs) transform dynamically in soil and plant tissues, releasing molybdenum (Mo) and sulfur (S) that can be incorporated gradually into the key enzymes involved in nitrogen metabolism and the antioxidant system, while the rest remain intact and act as nanozymes. Notably, there is 247.9 mg/kg of organic Mo in the nodule, while there is only 49.9 mg/kg of MoS2 NPs. This study demonstrates that it is the transformation that leads to the multifunctionality of MoS2, which can improve the biological nitrogen fixation (BNF) and growth. Therefore, MoS2 NPs enable a 30% increase in yield compared to the traditional molybdenum fertilizer (Na2MoO4). Excessive transformation of MoS2 nanosheets (NS) leads to the overaccumulation of Mo and sulfate in the plant, which damages the nodule function and yield. The study highlights the importance of understanding the transformation of nanomaterials for agricultural applications in future studies.

A broad-taxa approach as an important concept in ecotoxicological studies and pollution monitoring.

Aquatic invertebrates play a pivotal role in (eco)toxicological assessments because they offer ethical, cost-effective and repeatable testing options. Additionally, their significance in the food chain and their ability to represent diverse aquatic ecosystems make them valuable subjects for (eco)toxicological studies. To ensure consistency and comparability across studies, international (eco)toxicology guidelines have been used to establish standardised methods and protocols for data collection, analysis and interpretation. However, the current standardised protocols primarily focus on a limited number of aquatic invertebrate species, mainly from Arthropoda, Mollusca and Annelida. These protocols are suitable for basic toxicity screening, effectively assessing the immediate and severe effects of toxic substances on organisms. For more comprehensive and ecologically relevant assessments, particularly those addressing long-term effects and ecosystem-wide impacts, we recommended the use of a broader diversity of species, since the present choice of taxa exacerbates the limited scope of basic ecotoxicological studies. This review provides a comprehensive overview of (eco)toxicological studies, focusing on major aquatic invertebrate taxa and how they are used to assess the impact of chemicals in diverse aquatic environments. The present work supports the use of a broad-taxa approach in basic environmental assessments, as it better represents the natural populations inhabiting various ecosystems. Advances in omics and other biochemical and computational techniques make the broad-taxa approach more feasible, enabling mechanistic studies on non-model organisms. By combining these approaches with in vitro techniques together with the broad-taxa approach, researchers can gain insights into less-explored impacts of pollution, such as changes in population diversity, the development of tolerance and transgenerational inheritance of pollution responses, the impact on organism phenotypic plasticity, biological invasion outcomes, social behaviour changes, metabolome changes, regeneration phenomena, disease susceptibility and tissue pathologies. This review also emphasises the need for harmonised data-reporting standards and minimum annotation checklists to ensure that research results are findable, accessible, interoperable and reusable (FAIR), maximising the use and reusability of data. The ultimate goal is to encourage integrated and holistic problem-focused collaboration between diverse scientific disciplines, international standardisation organisations and decision-making bodies, with a focus on transdisciplinary knowledge co-production for the One-Health approach.

Design and Synthesis of a Water-Based Nanodelivery Pesticide System for Improved Efficacy and Safety.

Developing an environmentally friendly and safe nanodelivery system is crucial to improve the efficacy of pesticides and minimize environmental and health risks. However, preparing a completely water-based nanopesticide without using harmful solvents is a technical challenge. In this study, a water-based nanodelivery pesticide system was constructed to improve the efficacy and safety of Emamectin Benzoate (EB). A specific surfactant, 29-(4-(5-hydroxynonan-5-yl)phenoxy)-3,6,9,12,15,18,21,24,27-nonaoxanonacosan-1-ol (SurEB) was designed and synthesized to form a water-based nanodelivery system (EBWNS) with EB. Molecular dynamics simulations revealed the self-assembly and interaction forces between SurEB and EB in water, providing insights into the formation mechanism of EBWNS nanoparticles. The nanodelivery system showed the prolonged effectivity of EB with reduced degradation and demonstrated a good control efficacy for multiple target pests, such as red spider mite, beet armyworm larvae (Lepidoptera: Noctuidae), and rice stem borers (Chilo suppressalis). Toxicology tests on various objects demonstrated that the EBWNS has low toxicity for seeds, HaCaT cells, zebrafish, earthworm, and E. coli. This study provides a distinctive perspective for developing environmentally friendly nanopesticide formulations, which clarified a water-based treatment method for specific lipid-soluble pesticides. The water-based nanodelivery pesticide system has the potential to improve the efficacy and safety of pesticides in the process of field applications.

Nanoenabled Enhancement of Plant Tolerance to Heat and Drought Stress on Molecular Response.

Global warming has posed significant pressure on agricultural productivity. The resulting abiotic stresses from high temperatures and drought have become serious threats to plants and subsequent global food security. Applying nanomaterials in agriculture can balance the plant's oxidant level and can also regulate phytohormone levels and thus maintain normal plant growth under heat and drought stresses. Nanomaterials can activate and regulate specific stress-related genes, which in turn increase the activity of heat shock protein and aquaporin to enable plants' resistance against abiotic stresses. This review aims to provide a current understanding of nanotechnology-enhanced plant tolerance to heat and drought stress. Molecular mechanisms are explored to see how nanomaterials can alleviate abiotic stresses on plants. In comparison with organic molecules, nanomaterials offer the advantages of targeted transportation and slow release. These advantages help the nanomaterials in mitigating drought and heat stress in plants.

Correction: Recent trends in carbon nanotube (CNT)-based biosensors for the fast and sensitive detection of human viruses: a critical review.

[This corrects the article DOI: 10.1039/D2NA00236A.].

Advanced nanopesticides: Advantage and action mechanisms.

The use of various chemical substances to control pests, diseases, and weeds in the field is a necessary part of the agricultural development process in every country. While the application of pesticides can improve the quality and yield of crops, plant resistance and the harm caused by pesticide residues to the environment and humans have led to the search for greener and safer pesticide formulations to improve the current situation. In recent years, nanopesticides (NPts) have shown great potential in agriculture due to their high efficiency, low toxicity, targeting, resistance, and controlled slow release demonstrated in the experimental stage. Commonly used approaches to prepare NPts include the use of nanoscale metal materials as active ingredients (AI) (ingredients that can play a role in insecticide, sterilization and weeding) or the construction of carriers based on commonly used pesticides to make them stable in nano-sized form. This paper systematically summarizes the advantages and effects of NPts over conventional pesticides, analyzes the formation and functions of NPts in terms of structure, AI, and additives, and describes the mechanism of action of NPts. Despite the feasibility of NPts use, there is not enough comprehensive research on NPts, which must be supplemented by more experiments in terms of biotoxicology and ecological effects to provide strong support for NPts application.

Exceptional photo-elimination of antibiotic by a novel Z-scheme heterojunction catalyst composed of nanoscale zero valent iron embedded with carbon quantum dots (CQDs)-black TiO2.

Passivation of nanoscale zero valent iron (nZVI, Fe0) impaired its longevity while black TiO2 (b-TiO2) suffered from restricted optical properties. Using a facile approach, a novel Z-scheme heterojunction catalyst (Fe0@CQDs-TiO2(b)) of nZVI decorated with carbon quantum dots (CQDs) implanted into b-TiO2 was designed. Characterization results revealed the optical potential of the passivation coating of nZVI. The incorporation of CQDs stimulated the creation of active •OH during the dark reaction, and led to an accelerated mobility of photo-excited carriers of b-TiO2 and optimized its band gap (narrowing from 2.36 eV to 2.15 eV) during the light reaction. The photo-elimination capacity of metronidazole (MNZ) on Fe0@CQDs-TiO2(b) (99.36%) was 2.64, 8.25 and 1.34 fold beyond that on nZVI, b-TiO2 and Fe0@b-TiO2, respectively. The assembled material offered excellent adaptability to environmental substrates, in addition to being virtually unaffected by tap (95.62%) and river water (92.62%). The mechanism of MNZ degradation was elaborated, and the combination of density functional theory (DFT) calculations and LC-MS discerned 12 intermediates and 3 routes. Toxicity assessment of these products was conducted to ensure no inadvertent negative environmental impacts arose. This work proposed an original direction and mechanism for the application of passivation layers in nZVI-based materials for environmental restoration.

Construction of urchin-like core-shell Fe/Fe2O3@UiO-66 hybrid for effective tetracycline reduction and photocatalytic oxidation.

Although Fe/Fe2O3 has potential application compared with nanoscale zero-valent iron (nZVI), its smooth structure largely limits the catalytic performance. To address this challenge, we innovatively constructed highly efficient composite Fe/Fe2O3@UiO-66 via employing an urchin-like core-shell structure of Fe/Fe2O3 onto UiO-66 through a facile ion exchange precipitation method without inert gas protection. The characterization results show the urchin-like core-shell configuration can extend the life span of Fe0 and produce more active sites. Besides, the absorption spectrum is broadened by Fe2O3 which has narrow band gap and the high-efficiency separation of photogenerated electron-hole pairs is obtained with the load of Fe/Fe2O3. Moreover, Two-parameter pseudo-first-order decay model fits well with the reduction and adsorption of composites in the dark reaction, and a plausible pathway for tetracycline (TC) degradation is also proposed. The findings of this research provide a promising method for promoting the catalytic properties of MOF-based materials and Fe/Fe2O3.

In vitro toxicity and lung cancer risk: Atmospheric particulate matter from a city in southeastern Brazil impacted by biomass burning.

The effects of PM10 on human health were investigated using samples collected in São Carlos city (São Paulo state), by the determination of the concentrations of PAHs and derivatives, together with evaluations of cytotoxicity and the formation of ROS in in vitro tests. In 2016, the mean concentrations of PM10, ΣPAHs, Σoxy-PAHs, Σnitro-PAHs, Σsaccharides, and Σions were 21.12 ± 9.90 µg m-3, 1.47 ± 1.70 ng m-3, 0.37 ± 0.31 ng m-3, 0.84 ng m-3, 119.91 ± 62.14 ng m-3, and 5.66 ± 4.52 µg m-3, respectively. The PM10 concentrations did not exceed the limit thresholds set by national legislation, however, the annual lung cancer risk calculated was 2.59 ± 1.22 cases per 100,000 people, in the dry season, which accounts for the annual risk (April to September). Moreover, the carcinogenic activities of the PAHs mixture were more than 1000-fold higher in the dry season (dry season: BaPeq = 0.30 ng m-3; wet season BaPeq = 0.02 ng m-3). The concentrations of most analytes were also higher during the dry season, as had already been demonstrated in the same city. This was due to reductions in precipitation, relative humidity and air temperature, and increased biomass burning, which was the main source of PM10 in the city in 2016 (contribution rate of more than 50%). Toxicological results also showed the negative impacts of PM10, exposure to PM10 extracts for 72 h reduced the viability of A549 and MRC5 cells, and the formation of ROS was observed. The cellular responses obtained using combined and individual extracts of PM10 differed and were sometimes associated with specific compounds. These demonstrate the importance of monitoring PM toxicity using different approaches and the main anthropogenic sources' contribution. Therefore, to improve air quality and human health, existing legislation needs to be modified to incorporate these tests.

Molybdenum Nanofertilizer Boosts Biological Nitrogen Fixation and Yield of Soybean through Delaying Nodule Senescence and Nutrition Enhancement.

Soybean (Glycine max) is a crop of global significance and has low reliance on N fertilizers due to its biological nitrogen fixation (BNF) capacity, which harvests ambient N2 as a critical ecosystem service. BNF can be severely compromised by abiotic stresses. Enhancing BNF is increasingly important not only to alleviate global food insecurity but also to reduce the environmental impact of agriculture by decreasing chemical fertilizer inputs. However, this has proven challenging using current genetic modification or bacterial nodulation methods. Here, we demonstrate that a single application of a low dose (10 mg/kg) of molybdenum disulfide nanoparticles (MoS2 NPs) can enhance soybean BNF and grain yield by 30%, compared with conventional molybdate fertilizer. Unlike molybdate, MoS2 NPs can more sustainably release Mo, which then is effectively incorporated as a cofactor for the synthesis of nitrogenase and molybdenum-based enzymes that subsequently enhance BNF. Sulfur is also released sustainably and incorporated into biomolecule synthesis, particularly in thiol-containing antioxidants. The superior antioxidant enzyme activity of MoS2 NPs, together with the thiol compounds, protect the nodules from reactive oxygen species (ROS) damage, delay nodule aging, and maintain the BNF function for a longer term. The multifunctional nature of MoS2 NPs makes them a highly effective strategy to enhance plant tolerance to abiotic stresses. Given that the physicochemical properties of nanomaterials can be readily modulated, material performance (e.g., ROS capturing capacity) can be further enhanced by several synthesis strategies. This study thus demonstrates that nanotechnology can be an efficient and sustainable approach to enhancing BNF and crop yield under abiotic stress and combating global food insecurity.

Airborne fine particles drive H1N1 viruses deep into the lower respiratory tract and distant organs.

Mounting data suggest that environmental pollution due to airborne fine particles (AFPs) increases the occurrence and severity of respiratory virus infection in humans. However, it is unclear whether and how interactions with AFPs alter viral infection and distribution. We report synergetic effects between various AFPs and the H1N1 virus, regulated by physicochemical properties of the AFPs. Unlike infection caused by virus alone, AFPs facilitated the internalization of virus through a receptor-independent pathway. Moreover, AFPs promoted the budding and dispersal of progeny virions, likely mediated by lipid rafts in the host plasma membrane. Infected animal models demonstrated that AFPs favored penetration of the H1N1 virus into the distal lung, and its translocation into extrapulmonary organs including the liver, spleen, and kidney, thus causing severe local and systemic disorders. Our findings revealed a key role of AFPs in driving viral infection throughout the respiratory tract and beyond. These insights entail stronger air quality management and air pollution reduction policies.

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.

Nickel Oxide Nanoparticles Improve Soybean Yield and Enhance Nitrogen Assimilation.

Nickel (Ni) is a trace element beneficial for plant growth and development and could improve crop yield by stimulating urea decomposition and nitrogen-fixing enzyme activity. A full life cycle study was conducted to compare the long-term effects of soil-applied NiO nanoparticles (n-NiO), NiO bulk (b-NiO), and NiSO4 at 10-200 mg kg-1 on plant growth and nutritional content of soybean. n-NiO at 50 mg kg-1 significantly promoted the seed yield by 39%. Only 50 mg kg-1 n-NiO promoted total fatty acid content and starch content by 28 and 19%, respectively. The increased yield and nutrition could be attributed to the regulatory effects of n-NiO, including photosynthesis, mineral homeostasis, phytohormone, and nitrogen metabolism. Furthermore, n-NiO maintained a Ni2+ supply for more extended periods than NiSO4, reducing potential phytotoxicity concerns. Single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) for the first time confirmed that the majority of the Ni in seeds is in ionic form, with only 28-34% as n-NiO. These findings deepen our understanding of the potential of nanoscale and non-nanoscale Ni to accumulate and translocate in soybean, as well as the long-term fate of these materials in agricultural soils as a strategy for nanoenabled agriculture.