No abstract

Nanoenabled foliar-applied agrochemicals can potentially be safer and more efficient than conventional products. However, limited understanding about how nanoparticle properties influence their interactions with plant leaves, uptake, translocation through the mesophyll to the vasculature, and transport to the rest of the plant prevents rational design. This study used a combination of Au quantification and spatial analysis to investigate how size (3, 10, or 50 nm) and coating chemistry (PVP versus citrate) of gold nanoparticles (AuNPs) influence these processes. Following wheat foliar exposure to AuNPs suspensions (∼280 ng per plant), adhesion on the leaf surface was increased for smaller sizes, and PVP-AuNPs compared to citrate-AuNPs. After 2 weeks, there was incomplete uptake of citrate-AuNPs with some AuNPs remaining on the outside of the cuticle layer. However, the fraction of citrate-AuNPs that had entered the leaf was translocated efficiently to the plant vasculature. In contrast, for similar sizes, virtually all of the PVP-AuNPs crossed the cuticle layer after 2 weeks, but its transport through the mesophyll cells was lower. As a consequence of PVP-AuNP accumulation in the leaf mesophyll, wheat photosynthesis was impaired. Regardless of their coating and sizes, the majority of the transported AuNPs accumulated in younger shoots (10−30%) and in roots (10−25%), and 5−15% of the NPs <50 nm were exuded into the rhizosphere soil. A greater fraction of larger sizes AuNPs (presenting lower ζ potentials) was transported to the roots. The key hypotheses about the NPs physical−chemical and plant physiology parameters that may matter to predict leaf-to-rhizosphere transport are also discussed.

Nanoparticle zeta potentials are easy to measure and proposed as a required property for complete nanoparticle characterization, but relevant metadata must be reported with zeta potential to be scientifically useful.

radionuclides. [12][13][14][15][16][17] However, NZVI is an indiscriminate reductant that also readily reduces water to form hydrogen gas (Fe 0 + 2H 2 O → Fe 2+ + 2OH − + H 2(g) ). [18] This unwanted side reaction consumes the reducing capacity of the NZVI, decreasing its reactive lifetime, and increases the amount and cost of NZVI required for remediation. Several approaches have been proposed to increase the reactivity or stability of NZVI during remediation, including encapsulating them with polymers or into silica matrices, [15,19] doping them with noble metals like Pd or Pt, [20,21] and supporting them onto carbon matrices like carbon nanotubes or graphene. [22,23] While these approaches improve the injectability of the materials into the subsurface, none have improved the selectivity of NZVI for contaminants over water while still maintaining high reactivity with the target groundwater contaminants. An ideal material for groundwater remediation should possess both high reactivity and selectivity, [24] where the contaminant outcompetes water for reactive sites.Recently, it was shown by us and others that the sulfidation of NZVI lowers its reactivity with water and other non-target hydrophilic contaminants (e.g., NO 3 − ), while increasing its reactivity with target contaminants like chlorinated solvents Sulfidized nanoscale zerovalent iron (SNZVI) is a promising material for groundwater remediation. However, the relationships between sulfur content and speciation and the properties of SNZVI materials are unknown, preventing rational design. Here, the effects of sulfur on the crystalline structure, hydrophobicity, sulfur speciation, corrosion potential, and electron transfer resistance are determined. Sulfur incorporation extended the nano-Fe 0 BCC lattice parameter, reduced the Fe local vacancies, and lowered the resistance to electron transfer. Impacts of the main sulfur species (FeS and FeS 2 ) on hydrophobicity (water contact angles) are consistent with density functional theory calculations for these FeS x phases. These properties well explain the reactivity and selectivity of SNZVI during the reductive dechlorination of trichloroethylene (TCE), a hydrophobic groundwater contaminant. Controlling the amount and speciation of sulfur in the SNZVI made it highly reactive (up to 0.41 L m −2 d −1 ) and selective for TCE degradation over water (up to 240 moles TCE per mole H 2 O), with an electron efficiency of up to 70%, and these values are 54-fold, 98-fold, and 160-fold higher than for NZVI, respectively. These findings can guide the rational design of robust SNZVI with properties tailored for specific application scenarios.Highly redox active materials are an important tool for the degradation of refractory organic water and soil contaminants. [1][2][3][4][5][6][7] Nanoscale zero valent (NZVI) has been used for in situ groundwater remediation for more than two decades. [8][9][10][11][12] NZVI is a strong reductant that readily dechlorinates chlorinated solvents and antibiotics, and reduces and immobilizes h...

Sulfidized nanoscale zerovalent iron (SNZVI) has desirable properties for in situ groundwater remediation. However, there is limited understanding of how the sulfidation type and particle properties affect the reactivity and selectivity of SNZVI toward groundwater contaminants, or how reactivity changes as the particles age. Here, SNZVI synthesized by either a one-step (SNZVI-1) or two-step (SNZVI-2) process were characterized, and the reactivity of both fresh and aged (1d to 60 d) nanoparticles was assessed. The measured S/Fe ratio was 5.4 ± 0.5 mol % for SNZVI-1 and 0.8 ± 0.1 mol % for SNZVI-2. XPS analysis indicates S2–, S2 2–, and S n 2– species on the surface of both SNZVI-1 and SNZVI-2, while S2 2– is the dominant species inside of the SNZVI nanoparticles. SNZVI-1 particles were hydrophobic (contact angle = 103 ± 3°), while the other materials were hydrophilic (contact angles were 18 ± 2° and 36 ± 3° for NZVI and SNZVI-2, respectively). SNZVI-1, with greater S content and hydrophobicity, was less reactive with water than either NZVI or SNZVI-2 over a 60 d period, resulting in less H2 evolution. It also had the highest reactivity with TCE and the lowest reactivity with nitrate, consistent with its higher hydrophobicity. In contrast, both NZVI and SNZVI-2 were reactive with both TCE and nitrate. Both types of SNZVI remained more reactive after aging in water over 60 d than NZVI. These data suggest that the properties of the SNZVI made from a one-step synthesis procedure may provide better reactivity, selectivity, and longevity than that made from a two-step process.

Climate change is increasing the severity and length of heat waves. Heat stress limits crop productivity and can make plants more sensitive to other biotic and abiotic stresses. New methods for managing heat stress are needed. Herein, we have developed ∼30 nm diameter poly­(acrylic acid)-block-poly­(N-isopropylacrylamide) (PAA-b-PNIPAm) star polymers with varying block ratios for temperature-programmed release of a model antimicrobial agent (crystal violet, CV) at plant-relevant pH. Hyperspectral-Enhanced Dark field Microscopy was used to investigate star polymer–leaf interactions and route of entrance. The majority of loaded star polymers entered plant leaves through cuticular and epidermis penetration when applied with the adjuvant Silwet L-77. Up to 43 wt % of star polymers (20 μL at 200 mg L–1 polymer concentration) applied onto tomato (Solanum lycopersicum) leaves translocated to other plant compartments (younger and older shoots, stem, and root) over 3 days. Without Silwet L-77, the star polymers penetrated the cuticle, but mainly accumulated at the epidermis cell layer. The degree of the star polymer temperature responsiveness for CV release in vitro in the range of 20 to 40 °C depends on pH and the ratio of the PAA to PNIPAm blocks. Temperature-responsive release of CV was also observed in vivo in tomato leaves. These results underline the potential for PAA-b-PNIPAm star polymers to provide efficient and temperature-programmed delivery of cationic agrochemicals into plants for protection against heat stress.

No abstract

There is increasing pressure on global agricultural systems due to higher food demand, climate change, and environmental concerns. The design of nanostructures is proposed as one of the economically viable technological solutions that can make agrochemical use (fertilizers and pesticides) more efficient through reduced runoff, increased foliar uptake and bioavailability, and decreased environmental impacts. However, gaps in knowledge about the transport of nanoparticles across the leaf surface and their behavior in planta limit the rational design of nanoparticles for foliar delivery with controlled fate and limited risk. Here, the current literature on nano-objects deposited on leaves is reviewed. The different possible foliar routes of uptake (stomata, cuticle, trichomes, hydathodes, necrotic spots) are discussed, along with the paths of translocation, via the phloem, from the leaf to the end sinks (mature and developing tissues, roots, rhizosphere). This review details the interplays between morphological constraints, environmental stimuli, and physical-chemical properties of nanoparticles influencing their fate, transformation, and transport after foliar deposition. A metadata analysis from the existing literature highlighted that plant used for testing nanoparticle fate are most often dicotyledon plants (75%), while monocotyledons (as cereals) are less considered. Correlations on parameters calculated from the literature indicated that nanoparticle dose, size, zeta potential, and affinity to organic phases correlated with leaf-to-sink translocation, demonstrating that targeting nanoparticles to specific plant compartments by design should be achievable. Correlations also showed that time and plant growth seemed to be drivers for in planta mobility, parameters that are largely overlooked in the literature. This review thus highlights the material design opportunities and the knowledge gaps for targeted, stimuli driven deliveries of safe nanomaterials for agriculture.