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

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.

Influence of CuO Nanoparticle Aspect Ratio and Surface Charge on Disease Suppression in Tomato (Solanum lycopersicum).

Nanoparticles (NPs) have been shown to deliver micronutrients to plants to improve health, increase biomass, and suppress disease. Nanoscale properties such as morphology, size, composition, and surface chemistry have all been shown to impact nanomaterial interactions with plant systems. An organic-ligand-free synthesis method was used to prepare positively charged copper oxide (CuO) nanospikes, negatively charged CuO nanospikes, and negatively charged CuO nanosheets with exposed (001) crystal faces. X-ray photoelectron spectroscopy measurements show that the negative charge correlates to increased surface concentration of O on the NP surface, whereas relatively higher Cu concentrations are observed on the positively charged surfaces. The NPs were then used to treat tomato (Solanum lycopersicum) grown in soil infested with Fusarium oxysporum f. sp. lycopersici under greenhouse conditions. The negatively charged CuO significantly reduced disease progression and increased biomass, while the positively charged NPs and a CuSO4 salt control had little impact on the plants. Self-assembled monolayers were used to mimic the leaf surface to understand the intermolecular interactions between the NPs and the plant leaf; the data demonstrate that NP electrostatics and hydrogen-bonding interactions play an important role in adsorption onto leaf surfaces. These findings have important implications for the tunable design of materials as a strategy for the use of nano-enabled agriculture to increase food production.

Surface Coated Sulfur Nanoparticles Suppress Fusarium Disease in Field Grown Tomato: Increased Yield and Nutrient Biofortification.

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.

Role of Foliar Biointerface Properties and Nanomaterial Chemistry in Controlling Cu Transfer into Wild-Type and Mutant Arabidopsis thaliana Leaf Tissue.

Seven Arabidopsis thaliana mutants with differences in cuticle thickness and stomatal density were foliar exposed to 50 mg L-1 Cu3(PO4)2 nanosheets (NS), CuO NS, CuO nanoparticles, and CuSO4. 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.

Advanced material modulation of nutritional and phytohormone status alleviates damage from soybean sudden death syndrome.

Customized Cu3(PO4)2 and CuO nanosheets and commercial CuO nanoparticles were investigated for micronutrient delivery and suppression of soybean sudden death syndrome. An ab initio thermodynamics approach modelled how material morphology and matrix effects control the nutrient release. Infection reduced the biomass and photosynthesis by 70.3 and 60%, respectively; the foliar application of nanoscale Cu reversed this damage. Disease-induced changes in the antioxidant enzyme activity and fatty acid profile were also alleviated by Cu amendment. The transcription of two dozen defence- and health-related genes correlates a nanoscale Cu-enhanced innate disease response to reduced pathogenicity and increased growth. Cu-based nanosheets exhibited a greater disease suppression than that of CuO nanoparticles due to a greater leaf surface affinity and Cu dissolution, as determined computationally and experimentally. The findings highlight the importance and tunability of nanomaterial properties, such as morphology, composition and dissolution. The early seedling foliar application of nanoscale Cu to modulate nutrition and enhance immunity offers a great potential for sustainable agriculture.

Copper Nanomaterial Morphology and Composition Control Foliar Transfer through the Cuticle and Mediate Resistance to Root Fungal Disease in Tomato (Solanum lycopersicum).

Two copper nanomaterials (CuO nanoparticles [NPs] and Cu3(PO4)2·3H2O nanosheets) and CuSO4 were applied to tomato (Solanum lycopersicum) leaves, and elemental Cu movement from the leaf surface through the cuticle and into the interior leaf tissue was monitored over 8 h. Two forms of nanoscale Cu were used to foliar treat tomato on a weekly basis in greenhouse and field experiments in the presence of the pathogen Fusarium oxysporum f. sp. lycopersici. For CuSO4, Cu accumulation and retention in the cuticle was over 7-fold greater than the nanomaterials, demonstrating that nanoscale morphology and composition mediate Cu accumulation in leaf tissue. In the greenhouse, weekly foliar applications of the nanosheets and NPs increased seedling biomass by 90.9 and 93.3%, respectively, compared to diseased and ionic Cu controls. In the field, Cu3(PO4)2·3H2O nanosheets reduced disease progress by 26.0% and significantly increased fruit yield by over 45.5% per plant relative to the other treatments in diseased soil. These findings suggest that nanoscale nutrient chemical properties can be tuned to maximize and control movement through the cuticle and that interactions at the seedling leaf biointerface can lead to season-long benefit for tomato growing in the presence of Fusarium spp.

Cobalt Release from a Nanoscale Multiphase Lithiated Cobalt Phosphate Dominates Interaction with Shewanella oneidensis MR-1 and Bacillus subtilis SB491.

Cobalt phosphate engineered nanomaterials (ENMs) are an important class of materials that are used as lithium ion battery cathodes, catalysts, and potentially as super capacitors. As production of these nanomaterials increases, so does the likelihood of their environmental release; however, to date, there are relatively few investigations of the impact of nanoscale metal phosphates on biological systems. Furthermore, nanomaterials used in commercial applications are often multiphase materials, and analysis of the toxic potential of mixtures of nanomaterials has been rare. In this work, we studied the interactions of two model environmental bacteria, Shewanella oneidensis MR-1 and Bacillus subtilis, with a multiphase lithiated cobalt phosphate (mLCP) nanomaterial. Using a growth-based viability assay, we found that mLCP was toxic to both bacteria used in this study. To understand the observed toxicity, we screened for production of reactive oxygen species (ROS) and release of Co2+ from mLCP using three abiotic fluorophores. We also used Newport Green DCF dye to show that cobalt was taken up by the bacteria after mLCP exposure. Using transmission electron microscopy, we noted that the mLCP was not associated with the bacterial cell surface. In order for us to further probe the mechanism of interaction of mLCP, the bacteria were exposed to an equivalent dose of cobalt ions that dissolved from mLCP, which recapitulated the changes in viability when the bacteria were exposed to mLCP, and it also recapitulated the observed bacterial uptake of cobalt. Taken together, this implicates the release of cobalt ions and their subsequent uptake by the bacteria as the major toxicity mechanism of mLCP. The properties of the ENM govern the release rate of cobalt, but the toxicity does not arise from nanospecific effects-and importantly, the chemical composition of the ENM may dictate the oxidation state of the metal centers and thus limit ROS production.

Impact of lithiated cobalt oxide and phosphate nanoparticles on rainbow trout gill epithelial cells.

Metal oxide and phosphate nanoparticles (NPs) are ubiquitous in emerging applications, ranging from energy storage to catalysis. Cobalt-containing NPs are particularly important, where their widespread use raises questions about the relationship between composition, structure, and potential for environmental impacts. To address this gap, we investigated the effects of lithiated metal oxide and phosphate NPs on rainbow trout gill epithelial cells, a model for environmental exposure. Lithium cobalt oxide (LCO) NPs significantly reduced cell viability at10 µg/mL, while a 10-fold higher concentration of lithiated cobalt hydroxyphosphate (LCP) NPs was required to significantly reduce viability. Exposure to Li+ and Co2+ alone, at concentrations relevant to ion released from the NPs, did not reduce cell viability and minimally impacted reactive oxygen species (ROS) levels. Both LCO- and LCP-NPs were found within membrane-bound organelles. However, only LCP-NPs underwent rapid and complete dissolution in artificial lysosomal fluid. Unlike LCP-NPs, LCO-NPs significantly increased intracellular ROS, could be found within abnormal multilamellar bodies, and induced formation of intracellular vacuoles. Increased p53 gene expression, measured in individual cells, was observed at sub-toxic concentrations of both LCO- and LCP-NPs, implicating both in inductions of cellular damage and stress at concentrations approaching predicted environmental levels. Our results implicate the intact NP, not the dissolved ions, in the observed adverse effects and show that LCO-NPs significantly impact cell viability accompanied by increase in intracellular ROS and formation of organelles indicative of cell stress, while LCP-NPs have minimal adverse effects, possibly due to their rapid dissolution in acidic organelles.

Photochemistry of nitrate chemisorbed on various metal oxide surfaces.

Atmospheric aerosols are known to provide an important surface for gas-solid interfaces that can lead to heterogeneous reactions impacting tropospheric chemistry. In this work, α-Fe2O3, TiO2, γ-Al2O3, SiO2 and ZnO, common components of atmospheric aerosols, served as models to investigate the gas-solid interface of nitric acid with aerosols in the presence of simulated solar radiation. Adsorbed nitrate and gaseous products can be continuously monitored with infrared spectroscopy (IR). Kinetic studies of adsorbed species were carried out using attenuated total reflectance infrared spectroscopy (ATR-FTIR). Ex situ simultaneous infrared spectroscopy of gas-phase products using a 2 m long path cell allowed the detection of gaseous products at early stages of the heterogeneous photochemical reaction. In addition, photoactive gaseous products, such as HONO, were detected as gas analysis was carried out outside the region of irradiation. All reactions were found to be first order with respect to adsorbed nitric acid and yielded gas-phase products such as NO, NO2, N2O4, N2O, and HONO. While the correlation between semiconductor properties of the metal oxide and the heterogeneous photochemical rate constant (j) is not direct, the semiconductor properties were found to play a role in the formation of relatively high proportions of greenhouse gas nitrous oxide (N2O).