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Nanoenabled strategies have recently attracted attention as a sustainable platform for agricultural applications. Here, we present a mechanistic understanding of nanobiointeraction through an orthogonal investigation. Pristine (nS) and stearic acid surface-modified (cS) sulfur nanoparticles (NPs) as a multifunctional nanofertilizer were applied to tomato ( Solanum lycopersicum L.) through soil. Both nS and cS increased root mass by 73% and 81% and increased shoot weight by 35% and 50%, respectively, compared to the untreated controls. Bulk sulfur (bS) and ionic sulfate (iS) had no such stimulatory effect. Notably, surface modification of S NPs had a positive impact, as cS yielded 38% and 51% greater shoot weight compared to nS at 100 and 200 mg/L, respectively. Moreover, nS and cS significantly improved leaf photosynthesis by promoting the linear electron flow, quantum yield of photosystem II, and relative chlorophyll content. The time-dependent gene expression related to two S bioassimilation and signaling pathways showed a specific role of NP surface physicochemical properties. Additionally, a time-dependent Global Test and machine learning strategy applied to understand the NP surface modification domain metabolomic profiling showed that cS increased the contents of IA, tryptophan, tomatidine, and scopoletin in plant leaves compared to the other treatments. These findings provide critical mechanistic insights into the use of nanoscale sulfur as a multifunctional soil amendment to enhance plant performance as part of nanoenabled agriculture.

In the present study, experiments were conducted to assess the influence of nanoscale sulfur in the microbial community structure of metallophytes in Hg-contaminated rhizosphere soil for planting rapeseed. The results showed that the richness and diversity of the rhizobacteria community decreased significantly under Hg stress, but increased slightly after SNPs addition, with a reduction in the loss of Hg-sensitive microorganisms. Moreover, all changes in the relative abundances of the top ten phyla influenced by Hg treatment were reverted when subjected to Hg + SNPs treatment, except for Myxococcota and Bacteroidota. Similarly, the top five genera, whose relative abundance decreased the most under Hg alone compared to CK, increased by 19.05%-54.66% under Hg + SNPs treatment compared with Hg alone. Furthermore, the relative abundance of Sphingomonas , as one of the dominant genera for both CK and Hg + SNPs treatment, was actively correlated with plant growth. Rhizobacteria, like Pedobacter and Massilia , were significantly decreased under Hg + SNPs and were positively linked to Hg accumulation in plants. This study suggested that SNPs could create a healthier soil microecological environment by reversing the effect of Hg on the relative abundance of microorganisms, thereby assisting microorganisms to remediate heavy metal-contaminated soil and reduce the stress of heavy metals on plants.

Chromium (VI) is one of the hazardous heavy metal, heavily discharged into the soil and severely hampers the plants yield. The TiO 2 NPs was selected due to its potential to alleviate the heavy metals toxicity. This manuscript unravels the mechanisms for Cr(VI) induced toxicity and how foliar application of TiO 2 NP S potentially ameliorate the toxicity by regulating the photosynthetic attributes, DNA damage, antioxidants defense machinery, and phytochelatins synthesis in Helianthus annuus L. Plants were exposed to Cr(VI) concentrations [0, 15, 30, and 60 mg Cr(VI) kg -1 of soil], and TiO 2 NP S (15 mg L -1 , 25 nm size ) were foliar sprayed thrice to the plants at three days interval. The maximum accumulation of total chromium was recorded in root (12.53 µg g -1 DW) followed by shoot (5.67 µg g -1 DW) at 60 mg Cr(VI) treatment. The presence and localization of TiO 2 NPs inside the plant leaf cells were confirmed by TEM-EDS analysis. The results revealed that Cr(VI) exposure had a dose-dependent inhibitory effects on photosynthetic attributes, structure of guard and epidermal cells, photosynthetic pigments; inducing impacts on H 2 O 2 and MDA productions, DNA damage, AsA-GSH cycle, and most importantly on PC 2 , and PC 3 synthesis which is rarely reported. However, TiO 2 NPs exposure minimized Cr(VI) induced toxicity through reduction of total chromium accumulation, H 2 O 2 and MDA productions, thereby reducing DNA damage reported first time under combined treatment of Cr(VI)+ TiO 2 NPs as evidenced through comet assay. It also positively regulate the photosynthetic pigments, AsA-GSH cycle, and modulates PC 2 and PC 3 synthesis which have crucial impacts on ROS quenching and Cr(VI) detoxification, respectively, and in turn, minimizes Cr(VI) toxicity in H. annuus L. Besides, this study strengthens the less acknowledged report that Cr(VI) is an inducer of PCs synthesis and also confirms that TiO 2 NPs potentially counteract Cr(VI) toxicity., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Experiments were performed to explore the impact of sulfur nanoparticles (SNPs) on growth, Cu accumulation, and physiological and biochemical responses of oilseed rape (Brassica napus L.) inoculated with 5 mg/L Cu-amended MS medium supplemented with or without 300 mg/L SNPs exposure. Cu exerted severe phytotoxicity and inhibited plant growth. SNPs application enhanced the shoot height, root length, and dry weight of shoot and root by 34.6%, 282%, 41.7% and 37.1%, respectively, over Cu treatment alone, while the shoot and root Cu contents and Cu-induced lipid perodixation as the malondialdehyde (MDA) levels in shoots and roots were decreased by 37.6%, 35%, 28.4% and 26.8%. Further, the increases in superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), ascorbate peroxidase (APX), glutathione reductase (GR) and glutathione S-transferase (GST) enzyme activities caused by Cu stress were mitigated in shoots (10.9%-37.1%) and roots (14.6%-35.3%) with SNPs addition. SNPs also positively counteracted the negative effects on shoot K, Ca, P, Mg, Mn, Zn and Fe contents and root K, Ca, Mg and Mn contents from Cu exposure alone, and significantly promoted the nutrients accumulation in plant. Additionally, in comparison with common bulk sulfur particles (BSPs) and sulfate, SNPs showed more positive effects on promoting growth in shoots (6.7% and 19.5%) and roots (10.9% and 15.1%), as well as lowering the shoot Cu content (40.1% and 43.3%) under Cu stress. Thus, SNPs application has potential to be a green and sustainable technology for increasing plant productivity and reducing accumulation of toxic metals in heavy metal polluted soils., (Copyright © 2021. Published by Elsevier B.V.)

Little is known about the effect of nano sulfur (NS) under field conditions as a multifunctional agricultural amendment. Pristine and surface coated NS (CS) were amended in soil at 200 mg/kg that was planted with tomato ( Solanum lycopersicum ) and infested with Fusarium oxysporum f. sp. lycopersici . Foliar exposure of CS (200 μg/mL) was also included. In healthy plants, CS increased tomato marketable yield up to 3.3∼3.4-fold compared to controls. In infested treatments, CS significantly reduced disease severity compared to the other treatments. Foliar and soil treatment with CS increased yield by 107 and 192% over diseased controls, respectively, and significantly increased fruit Ca, Cu, Fe, and Mg contents. A $33/acre investment in CS led to an increase in marketable yield from 4920 to 11,980 kg/acre for healthy plants and from 1135 to 2180 kg/acre for infested plants, demonstrating the significant potential of this nanoenabled strategy to increase food production.

Widespread use of metal-based nanoparticles (NPs) may result in the increased accumulation of metals in agricultural soil, which could affect crop productivity and contaminate the food-chain. The effect of sulfur nanoparticles (S NPs, 200 mg/L) co-exposure on the toxicity of CuO nanoparticles (CuO NPs, 25 and 50 mg/L) to wheat seedlings was investigated in a hydroponic system. CuO NPs exposure significantly inhibited the growth of wheat seedlings, causing 43.6% and 54.1% decreases in the fresh biomass of plants and 82.8% and 83.1% decrease in the total chlorophyll contents at 25 and 50 mg/L (CuONP25 and CuONP50), respectively, as compared to controls. CuO NPs exposure at both concentrations increased the malondialdehyde (MDA) content in shoot and root tissues by 66.4-67.9% and 47.7-48.8%, respectively. Further, CuO NPs exposure elevated the activities POD, SOD, and CAT by 2.19-2.27, 5.82-6.09, and 1.44-1.95 times in roots, and by 45.2-67.8%, 86.7-154.5%, and 22.5-56.1% in shoot, respectively, in comparison to control. The addition of S NPs alone increased wheat biomass by 11.0% and total chlorophyll contents by 4.4%, compared to controls. Further, simultaneous exposure to S NPs (200 mg/L) and CuO NPs (25 or 50 mg/L) alleviated the CuO NPs toxicity; wheat biomass was 47.8% and 37.7% higher in CuONP25 + SNP and CuONP50 + SNP treatments, respectively, as compared to CuO NPs alone treated plants. Co-exposed plants showed reduced levels of total reactive oxygen species (ROS), O 2 ·- and H 2 O 2 . Additionally, S NPs exposure reduced Cu uptake and accumulation in both root and shoot tissue by 32.2-54.4% and 38.3-57.5%, respectively. In summary, S NPs alleviated CuO NPs toxicity to wheat seedlings, most likely by reducing Cu bioavailability and accumulation of Cu in plant tissues, and also altered S nutrition and the modulation of antioxidant response in plants. These results showed that S NPs application has the potential to alleviate CuO NP toxicity and increase wheat productivity affected by metals toxicity., Competing Interests: Declaration of competing interest Research support: This research received no external financial or non-financial support. Relationship: There is no additional relationship to disclose. Patents and intellectual property: There is no patent to disclose. Other activities: There are no additional activities to disclose., (Copyright © 2022. Published by Elsevier B.V.)

Seven Arabidopsis thaliana mutants with differences in cuticle thickness and stomatal density were foliar exposed to 50 mg L -1 Cu 3 (PO 4 ) 2 nanosheets (NS), CuO NS, CuO nanoparticles, and CuSO 4 . Three separate fractions of Cu (surface-attached, cuticle, interior leaf) were isolated from the leaf at 0.25, 2, 4, and 8 h. Cu transfer from the surface through the cuticle and into the leaf varied with mutant and particle type. The Cu content on the surface decreased significantly over 8 h but increased in the cuticle. Cu derived from the ionic form had the greatest cuticle concentration, suggesting greater difficulty in moving across this barrier and into the leaf. Leaf Cu in the increased-stomatal mutants was 8.5-44.9% greater than the decreased stomatal mutants, and abscisic acid to close the stomata decreased Cu in the leaf. This demonstrates the importance of nanomaterial entry through the stomata and enables the optimization of materials for nanoenabled agriculture.

In agriculture, loss of crop yield to pathogen damage seriously threatens efforts to achieve global food security. In the present work, "organic" elemental sulfur nanoparticles (SNPs) were investigated for management of the fungal pathogen Fusarium oxysporum f. sp. lycopersici on tomatoes. Foliar application and seed treatment with SNPs (30-100 mg/L, 30 and 100 nm) suppressed pathogen infection in tomatoes, in a concentration- and size-dependent fashion in a greenhouse experiment. Foliar application with 1 mg/plant of 30 nm SNPs (30-SNPs) exhibited the best performance for disease suppression, significantly decreasing disease incidence by 47.6% and increasing tomato shoot biomass by 55.6% after 10 weeks application. Importantly, the disease control efficacy with 30-SNPs was 1.43-fold greater than the commercially available fungicide hymexazol. Mechanistically, 30-SNPs activated the salicylic acid-dependent systemic acquired resistance pathway in tomato shoots and roots, with subsequent upregulation of the expression of pathogenesis-related and antioxidase-related genes (upregulated by 11-352%) and enhancement of the activity and content of disease-related biomolecules (enhanced by 5-49%). In addition, transmission electron microscopy imaging shows that SNPs were distributed in the tomato stem and directly inactivated in vivo pathogens. The oxidative stress in tomato shoots and roots, the root plasma membrane damage, and the growth of the pathogen in stem were all significantly decreased by SNPs. The findings highlight the significant potential of SNPs as an eco-friendly and sustainable crop protection strategy.

This study evaluates the bioaccumulation of unweathered (U) and weathered (W) CuO in NP, bulk and ionic form (0-400 mg/kg) by lettuce exposed for 70 d in soil co-contaminated with field incurred chlordane. To evaluate CuO trophic transfer, leaves were fed to crickets (Acheta domestica) for 15 d, followed by insect feeding to lizards (Anolis carolinensis). Upon weathering, the root Cu content of the NP treatment increased 214% (327 ± 59.1 mg/kg) over unaged treatment. Cu root content decreased in bulk and ionic treatments from 70-130 mg/kg to 13-26 mg/kg upon aging in soil. Micro X-ray fluorescence (μ-XRF) analysis of W-NP-exposed roots showed a homogenous distribution of Cu (and Ca) in the tissues. Additionally, micro X-ray absorption near-edge (μ-XANES) analysis of W-NP-exposed roots showed near complete transformation of CuO to Cu (I)-sulfur and oxide complexes in the tissues, whereas in unweathered treatment, most root Cu remained as CuO. The expression level of nine genes involved in Cu transport shows that the mechanisms of CuO NPs (and bulk) response/accumulation are different than ionic Cu. The chlordane accumulation by lettuce upon co-exposure to CuO NPs significantly increased upon weathering. Conversely, bulk and ionic exposures decreased pesticide accumulation by plant upon weathering. The Cu cricket fecal content from U-NP-exposed insects was significantly greater than the bulk or ion treatments, suggesting a higher initial NP accumulation followed by significantly greater elimination during depuration. In the lizard, Cu content in the intestine, body and head did not differ as a function of weathering. This study demonstrates that CuO NPs may undergo transformation processes in soil upon weathering that subsequently impact NPs availability in terrestrial food chains.

The effect of dissolved organic matter (DOM) on nanoparticle toxicity to plants is poorly understood. In this study, tannic acid (TA) was selected as a DOM surrogate to explore the mechanisms of neodymium oxide NPs (Nd2O3 NPs) phytotoxicity to pumpkin (Cucurbita maxima). The results from the tested concentrations showed that 100 mg L(-1) Nd2O3 NPs were significantly toxic to pumpkin in term of fresh biomass, and the similar results from the bulk particles and the ionic treatments were also evident. Exposure to 100 mg L(-1) of Nd2O3 NPs and BPs in 1/5 strength Hoagland's solution not only significantly inhibited pumpkin growth, but also decreased the S, Ca, K and Mg levels in plant tissues. However, 60 mg L(-1) TA significantly moderated the observed phytotoxicity, decreased Nd accumulation in the roots, and notably restored S, Ca, K and Mg levels in NPs and BPs treated pumpkin. TA at 60 mg L(-1) increased superoxide dismutase (SOD) activity in both roots (17.5%) and leaves (42.9%), and catalase (CAT) activity (243.1%) in the roots exposed to Nd2O3 NPs. This finding was confirmed by the observed up-regulation of transcript levels of SOD and CAT in Nd2O3 NPs treated pumpkin analyzed by quantitative reverse transcription polymerase chain reaction. These results suggest that TA alleviates Nd2O3 BPs/NPs toxicity through alteration of the particle surface charge, thus reducing the contact and uptake of NPs by pumpkin. In addition, TA promotes antioxidant enzymatic activity by elevating the transcript levels of genes involved in ROS scavenging. Our results shed light on the mechanisms underlying the influence of DOM on the bioavailability and toxicity of NPs to terrestrial plants.