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1. Nanoscale CuO charge and morphology control Fusarium suppression and nutrient biofortification in field-grown tomato and watermelon

   https://doi.org/10.1016/j.scitotenv.2023.167799  

   Deng, Chaoyi; Protter, Connor R.; Wang, Yi; Borgatta, Jaya; Zhou, Jingyi; Wang, Peiying; Goyal, Vinod; Brown, Hannah J.; Rodriguez-Otero, Kevin; Dimkpa, Christian O.; et al (December 2023, Science of The Total Environment)

   Limited data exist on how surface charge and morphology impact the effectiveness of nanoscale copper oxide (CuO) as an agricultural amendment under field conditions. This study investigated the impact of these factors on tomatoes and watermelons following foliar treatment with CuO nanosheets (NS-) or nanospikes (NP+ and NP-) exhibiting positive or negative surface charge. Results showed plant species-dependent benefits. Notably, tomatoes infected with Fusarium oxysporum had significantly reduced disease progression when treated with NS-. Watermelons benefited similarly from NP+. Although disease suppression was significant and trends indicated increased yield, the yield effects weren't statistically significant. However, several nanoscale treatments significantly enhanced the fruit's nutritional value, and this nano-enabled biofortification was a function of particle charge and morphology. Negatively charged nanospikes significantly increased the Fe content of healthy watermelon and tomato (20–28 %) and Ca in healthy tomato (66 %), compared to their positively charged counterpart. Negatively charged nanospikes also outperformed negatively charged nanosheets, leading to significant increases in the content of S and Mg in infected watermelon (37–38 %), Fe in healthy watermelon (58 %), and Ca (42 %) in healthy tomato. These findings highlight the potential of tuning nanoscale CuO chemistry for disease suppression and enhanced food quality under field conditions. 

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2. Copper oxide nanoparticle dissolution at alkaline pH is controlled by dissolved organic matter: influence of soil-derived organic matter, wheat, bacteria, and nanoparticle coating

   https://doi.org/10.1039/d0en00574f  

   Hortin, J. M.; Anderson, A. J.; Britt, D. W.; Jacobson, A. R.; McLean, J. E. (January 2020, Environmental Science: Nano)

   Dissolution of CuO nanoparticles, releasing Cu ions, is a primary mechanism of Cu interaction in the rooting zone of plants. CuO dissolution is sometimes incorrectly considered negligible at high pH, since complexation of Cu with dissolved organic matter may enhance nanoparticle dissolution. Therefore data on the effects of plant-microbial-soil interactions on nanoparticle dissolution, particularly in alkaline soils, are needed. Dissolution of CuO nanoparticles (100 mg kg −1 Cu) was studied in sand supplemented with factorial combinations of wheat growth, a root-colonizing bacterium, and saturated paste extracts (SPEs) from three alkaline, calcareous soils. In control sand systems with 3.34 mM Ca(NO 3 ) 2 solution, dissolved Cu was low (266 μg L −1 Cu). Addition of dissolved organic matter via wheat root metabolites and/or soil SPEs increased dissolved Cu to 795–6250 μg L −1 Cu. Dissolution was correlated with dissolved organic carbon ( R = 0.916, p < 0.0001). Ligands >3 kDa, presumably fulvic acid from the SPEs, complexed Cu driving solubility; the addition of plant exudates further increased solubility 1.5–3.5×. The root-colonizing bacterium decreased dissolved Cu in sand pore waters from planted systems due to metabolism of root exudates. Batch solubility studies (10 mg L −1 Cu) with the soil SPEs and defined solutions containing bicarbonate or fulvic acid confirmed elevated CuO nanoparticle solubility at >7.5 pH. Nanoparticle dissolution was suppressed in batch experiments compared to sand, via nanoparticle organic matter coating or homoconjugation of dissolved organic matter. Alterations of CuO nanoparticles by soil organic matter, plant exudates, and bacteria will affect dissolution and bioavailability of the CuO nanoparticles in alkaline soils. 

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3. Chitosan-Coated Mesoporous Silica Nanoparticles for Suppression of Fusarium virguliforme in Soybeans ( Glycine max )

   https://doi.org/10.1021/acsagscitech.4c00025  

   O’Keefe, Tana L.; Deng, Chaoyi; Wang, Yi; Mohamud, Sharmaka; Torres-Gómez, Andres; Tuga, Beza; Huang, Cheng-Hsin; Alvarez Reyes, Wilanyi R.; White, Jason C.; Haynes, Christy L. (May 2024, ACS Agricultural Science & Technology)

   There is a need to develop new and sustainable agricultural technologies to help provide global food security, and nanoscale materials show promising results in this area. In this study, mesoporous silica nanoparticles (MSNs) and chitosan-coated mesoporous silica nanoparticles (CTS-MSNs) were synthesized and applied to soybeans (Glycine max) by two different strategies in greenhouse and field studies to study the role of dissolved silicic acid and chitosan in enhancing plant growth and suppressing disease damage caused by Fusarium virguliforme. Plant growth and health were assessed by measuring the soybean biomass and chlorophyll content in both healthy and Fusarium-infected plants at harvest. In the greenhouse study, foliar and seed applications with 250 mg/L nanoparticle treatments were compared. A single seed treatment of MSNs reduced disease severity by 30% and increased chlorophyll content in both healthy and infected plants by 12%. Based on greenhouse results, seed application was used in the follow-up field study and MSNs and CTS-MSNs reduced disease progression by 12 and 15%, respectively. A significant 32% increase was observed for chlorophyll content for plants treated with CTS-MSNs. Perhaps most importantly, nanoscale silica seed treatment significantly increased (23–68%) the micronutrient (Zn, Mn, Mg, K, B) content of soybean pods, suggesting a potential sustainable strategy for nano-enabled biofortification to address nutrition insecurity. Overall, these findings indicate that MSN and CTS-MSN seed treatments in soybeans enable disease suppression and increase plant health as part of a nano-enabled strategy for sustainable agriculture. 

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4. Soil-derived fulvic acid and root exudates, modified by soil bacteria, alter CuO nanoparticle-induced root stunting of wheat via Cu complexation

   https://doi.org/10.1039/c9en00728h  

   Hortin, J. M.; Anderson, A. J.; Britt, D. W.; Jacobson, A. R.; McLean, J. E. (December 2019, Environmental Science: Nano)

   CuO nanoparticles (NPs) are explored as fungicides and fertilizers, and are increasingly likely to be applied to agricultural soils. Consequently, interactions of CuO NPs with soil pore water (SPW) components, plants, and microbes must be understood. These experiments examined whether dissolved natural organic matter (DNOM) from SPW, or root/bacterial exudates, changed wheat ( Triticum aestivum L. v. Deloris) responses to 100 mg kg −1 (Cu/sand) as CuO NPs. Seedlings were grown in sand with 3.34 mM Ca(NO 3 ) 2 or one of three SPWs, differing in DNOM concentration and composition. At 10 days post-germination, CuO NPs stunted roots by 59% in the 3.34 mM Ca(NO 3 ) 2 and 26–35% in the three SPWs compared to plants grown without NPs. Malate, citrate, gluconate, and 2′-deoxymugineic acid (DMA), were elevated 1.3 to 5-fold in the rhizosphere with CuO NPs present. Cu was bioavailable through metallo-organic complexes, including Cu–DMA and Cu–gluconate. Fulvic acid in SPWs mitigated CuO NP-induced wheat root shortening. Pseudomonas chlororaphis O6 eliminated malate and citrate in the rhizospheres, reduced rhizosphere dissolved Cu ∼18–66%, and reduced root Cu 39% across all SPWs while enhancing root stunting ∼17% more across all SPWs than non-inoculated wheat grown with CuO NPs. Thus, both SPW components and root microbial colonization influenced wheat responses to CuO NPs. These interactions are likely in agricultural soils with additional processes, such as ion sorption, to influence CuO NP phytotoxicity, highlighting the importance of considering not just the target plant, but soil properties and associated microbiomes when evaluating impacts of NPs in agricultural usage. 

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5. Biomolecular corona formation on CuO nanoparticles in plant xylem fluid

   https://doi.org/10.1039/D1EN00140J  

   Borgatta, Jaya R.; Lochbaum, Christian A.; Elmer, Wade H.; White, Jason C.; Pedersen, Joel A.; Hamers, Robert J. (January 2021, Environmental Science: Nano)

   null (Ed.)

   Biomolecular coatings (coronas) that form on nanomaterials have been widely investigated in animal and bacterial cell culture and in the extracellular and intracellular fluids of animals. Such coronas influence the distribution of nanoparticles within organisms, their uptake by cells, and their storage in intracellular compartments. Plants can be exposed to nanoparticles via either intentional application of nanomaterials in agriculture or inadvertently due, for example, to biosolids amendment of soils. Development of a mechanistic understanding of nanoparticle transport and fate within plants requires consideration of corona acquisition within plants, particularly within the vascular fluids that transport nanoparticles throughout plants. Here, we examine the interactions between copper oxide (CuO) nanoparticles and pumpkin xylem fluid to understand corona formation in an important part of the plant vasculature system. We used CuO nanoparticles because they have emerged as a promising micronutrient source for the suppression of fungal diseases. The corona was composed primarily of proteins, despite the higher abundance of carbohydrates in xylem fluid. We used X-ray photoelectron spectroscopy to determine the thickness of the protein corona. Polyacrylamide gel electrophoresis revealed that protein binding to the CuO nanoparticle surface was selective; the most abundant proteins in the corona were not the most abundant ones in the xylem fluid. We used in situ attenuated total reflectance Fourier-transform infrared spectroscopy to show that the protein–CuO NP interactions were quasi-irreversible, while carbohydrate–CuO interactions were reversible. Corona formation is expected to influence the distribution and transformation of nanomaterials in plants. 

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