High Aspect Ratio Polymer Nanocarriers for Gene Delivery and Expression in Plants.

Plant genetic engineering methods are critical for food security and biofuel production and to enable molecular farming. Here, we elucidated how polymeric high aspect ratio nanocarriers can enable DNA delivery to plants and transient expression. We demonstrated that a nanocarrier with 20 nm width, 80 nm length, and a polymer-to-DNA ratio of N/P = 3.

Towards realizing nano-enabled precision delivery in plants.

Nanocarriers (NCs) that can precisely deliver active agents, nutrients and genetic materials into plants will make crop agriculture more resilient to climate change and sustainable. As a research field, nano-agriculture is still developing, with significant scientific and societal barriers to overcome. In this Review, we argue that lessons can be learned from mammalian nanomedicine.

Diffusiophoretic Transport of Charged Colloids in Ionic Surfactant Gradients Entirely below versus Entirely above the Critical Micelle Concentration.

When placed in an ionic surfactant gradient, charged colloids will undergo diffusiophoresis at a velocity, = ∇ ln , where is the diffusiophoretic mobility and is the surfactant concentration. The diffusiophoretic mobility depends in part on the charges and diffusivities of the surfactants and their counterions. Since micellization decreases surfactant diffusivity and alters charge distributions in a surfactant solution, of charged colloids in ionic surfactant gradients may differ significantly when surfactant concentrations are above or below the critical micelle concentration (CMC).

Interaction of impinging marangoni fields.

Hypothesis: Surface tension gradient driven Marangoni flows originating from multiple sources are important to many industrial and medical applications, but the theoretical literature focuses on single surfactant sources. Understanding how two spreading surfactant sources interact allows insights from single source experiments to be applied to multi-source applications. Two key features of multi-source spreading - source translation and source deformation - can be explained by transport modeling of a two-source system.

Charge, Aspect Ratio, and Plant Species Affect Uptake Efficiency and Translocation of Polymeric Agrochemical Nanocarriers.

An incomplete understanding of how agrochemical nanocarrier properties affect their uptake and translocation in plants limits their application for promoting sustainable agriculture. Herein, we investigated how the nanocarrier aspect ratio and charge affect uptake and translocation in monocot wheat () and dicot tomato () after foliar application. Leaf uptake and distribution to plant organs were quantified for polymer nanocarriers with the same diameter (∼10 nm) but different aspect ratios (low (L), medium (M), and high (H), 10-300 nm long) and charges (-50 to +15 mV).

Effect of polymer/surfactant complexation on diffusiophoresis of colloids in surfactant concentration gradients.

Hypothesis: A concentration gradient of surfactants in the presence of polymers that non-covalently associate with surfactants will exhibit a continually varying distribution of complexes with different composition, charge, and size. Since diffusiophoresis of colloids suspended in a solute concentration gradient depends on the relaxation of the gradient and on the interactions between solutes and particles, polymer/surfactant complexation will alter the rate of diffusiophoresis driven by surfactant gradients relative to that observed in the same concentration gradient in the absence of polymers.

Experiments: A microfluidic device was used to measure diffusiophoresis of colloids suspended in solutions containing a gradient of sodium dodecylsulfate (SDS) in the presence or absence of a uniform concentration of Pluronic P123 poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) nonionic triblock copolymers.

Temperature-Responsive Bottlebrush Polymers Deliver a Stress-Regulating Agent for Prolonged Plant Heat Stress Mitigation.

Anticipated increases in the frequency and intensity of extreme temperatures will damage crops. Methods that efficiently deliver stress-regulating agents to crops can mitigate these effects. Here, we describe high aspect ratio polymer bottlebrushes for temperature-controlled agent delivery in plants.

Marangoni spreading time evolution and synergism in binary surfactant mixtures.

Hypothesis: Marangoni spreading driven by localized surfactant solution deposition previously has been studied only for single surfactant systems. For binary surfactant mixtures, interactions that generate surface tension synergism, a thermodynamic effect, may also synergistically enhance Marangoni spreading dynamics, introducing the concept of Marangoni synergism. Spreading dynamics and possible Marangoni synergism should depend not only on thermodynamic properties but also kinetic properties of the binary system.

Tuning chemotactic and diffusiophoretic spreading hydrodynamic flows.

The transport of microorganisms by chemotaxis is described by the same "log-sensing" response as colloids undergoing diffusiophoresis, despite their different mechanistic origins. We employ a recently-developed macrotransport theory to analyze the advective-diffusive transport of a chemotactic or diffusiophoretic colloidal species (both referred to as "colloids") in a circular tube under a steady pressure-driven flow (referred to as hydrodynamic flow) and transient solute gradient. First, we derive an exact solution to the log-sensing chemotactic/diffusiophoretic macrotransport equation.

Star Polymers with Designed Reactive Oxygen Species Scavenging and Agent Delivery Functionality Promote Plant Stress Tolerance.

Plant abiotic stress induces reactive oxygen species (ROS) accumulation in leaves that can decrease photosynthetic performance and crop yield. Materials that scavenge ROS and simultaneously provide nutrients are needed to manage this stress. Here, we incorporated both ROS scavenging and ROS triggered agent release functionality into an ∼20 nm ROS responsive star polymer (RSP) poly(acrylic acid)--poly((2-(methylsulfinyl)ethyl acrylate)--(2-(methylthio)ethyl acrylate)) (PAA--P(MSEA--MTEA)) that alleviated plant stress by simultaneous ROS scavenging and nutrient agent release.

Surfactant spreading on a deep subphase: Coupling of Marangoni flow and capillary waves.

Hypothesis: Surfactant-driven Marangoni spreading generates a fluid flow characterized by an outwardly moving "Marangoni ridge". Spreading on thin and/or high viscosity subphases, as most of the prior literature emphasizes, does not allow the formation of capillary waves. On deep, low viscosity subphases, Marangoni stresses may launch capillary waves coupled with the Marangoni ridge, and new dependencies emerge for key spreading characteristics on surfactant thermodynamic and kinetic properties.

Effect of a Surfactant Additive on Drug Transport and Distribution Uniformity After Aerosol Delivery to Lungs.

Inhaled drug delivery can be limited by heterogeneous dose distribution. An additive that would disperse drug over the internal surfaces of the lung after aerosol deposition could improve dosing uniformity and increase the treated area. Our previous studies demonstrated that surfactant additives can produce surface tension-driven (Marangoni) flows that effectively dispersed aerosol-delivered drugs over mucus surfaces.

pH-Dependent Interfacial Tension and Dilatational Modulus Synergism of Oil-Soluble Fatty Acid and Water-Soluble Cationic Surfactants at the Oil/Water Interface.

While the concept of interfacial tension synergism in surfactant mixtures is well established, little attention has been paid to the possibility of synergistic effects on the interfacial rheology of mixed surfactant systems. Furthermore, interfacial tension synergism is most often investigated for mixtures of surfactants residing in a single phase. Here, we define dilatational modulus synergism and report a study of interfacial tension isotherms and complex dilatational moduli for a binary surfactant system with the two surfactants accessing the oil/water interface from opposite sides.

Phosphate Polymer Nanogel for Selective and Efficient Rare Earth Element Recovery.

Demand for rare earth elements (REEs) is increasing, and REE production from ores is energy-intensive. Recovering REEs from waste streams can provide a more sustainable approach to help meet REE demand but requires materials with high selectivity and capacity for REEs due to the low concentration of REEs and high competing ion concentrations. Here, we developed a phosphate polymer nanogel (PPN) to selectively recover REEs from low REE content waste streams, including leached fly ash.

Star Polymer Size, Charge Content, and Hydrophobicity Affect their Leaf Uptake and Translocation in Plants.

Determination of how the properties of nanocarriers of agrochemicals affect their uptake and translocation in plants would enable more efficient agent delivery. Here, we synthesized star polymer nanocarriers poly(acrylic acid)--poly(2-(methylsulfinyl)ethyl acrylate) (PAA--PMSEA) and poly(acrylic acid)--poly((2-(methylsulfinyl)ethyl acrylate)--(2-(methylthio)ethyl acrylate)) (PAA--P(MSEA--MTEA)) with well-controlled sizes (from 6 to 35 nm), negative charge content (from 17% to 83% PAA), and hydrophobicity and quantified their leaf uptake, phloem loading, and distribution in tomato () plants 3 days after foliar application of 20 μL of a 1g L star polymer solution. In spite of their property differences, ∼30% of the applied star polymers translocated to other plant organs, higher than uptake of conventional foliar applied agrochemicals (<5%).

Surfactant Driven Marangoni Spreading in the Presence of Predeposited Insoluble Surfactant Monolayers.

When an insoluble surfactant is deposited on the surface of a thin fluid film, stresses induced by surface tension gradients drive Marangoni spreading across the subphase surface. The presence of a predeposited layer of an insoluble surfactant alters that spreading. In this study, the fluid film was aqueous, the predeposited insoluble surfactant was dipalmitoylphosphatidylcholine (DPPC), and the deposited insoluble surfactant was oleic acid.

Amphiphilic Thiol Polymer Nanogel Removes Environmentally Relevant Mercury Species from Both Produced Water and Hydrocarbons.

Technologies for removal of mercury from produced water and hydrocarbon phases are desired by oil and gas production facilities, oil refineries, and petrochemical plants. Herein, we synthesize and demonstrate the efficacy of an amphiphilic, thiol-abundant (11.8 wt % S, as thiol) polymer nanogel that can remove environmentally relevant mercury species from both produced water and the liquid hydrocarbon.

Depletion Forces Induced by Mixed Micelles of Nonionic Block Copolymers and Anionic Surfactants.

Depletion forces were measured between a silica sphere and a silica plate in solutions containing nonionic Pluronic P123 poly(ethylene oxide--propylene oxide--ethylene oxide) triblock copolymers and anionic sodium dodecyl sulfate (SDS) surfactants using colloidal probe atomic force microscopy. Prior research established synergistic depletion force enhancement in solutions containing SDS and unimeric Pluronic F108 block copolymers via formation of large pseudo-polyelectrolyte complexes. The current work addresses a more complex system where the polymer is above its critical micelle concentration, and surfactant binding alters not only the size and charge of the micelles but also the number of polymers per micelle.

Temperature- and pH-Responsive Star Polymers as Nanocarriers with Potential for Agrochemical Delivery.

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.

Advective-diffusive spreading of diffusiophoretic colloids under transient solute gradients.

We analytically calculate the one-dimensional advective-diffusive spreading of a point source of diffusiophoretic (DP) colloids, driven by the simultaneous diffusion of a Gaussian solute patch. The spreading of the DP colloids depends critically on the ratio of the DP mobility, M (which can be positive or negative), to the solute diffusivity, D. For instance, we demonstrate, for the first time, that solute-repelling colloids (M < 0) undergo long-time super-diffusive transport for M/D < -1.

Colloidal Depletion and Structural Force Synergism or Antagonism in Solutions of Mutually Repelling Polyelectrolytes and Ionic Surfactants.

Depletion and structural forces were measured between a silica sphere and plate in solutions containing sodium polyacrylate (Na-PAA) anionic polyelectrolyte and sodium dodecyl sulfate (SDS) anionic surfactant using colloidal probe atomic force microscopy, at high pH where the two species are electrostatically repelling from each other and from the silica surfaces. Measurements were performed for a range of SDS and Na-PAA concentrations to span conditions where only one of the species or both of the species would exert a detectable depletion or structural force when present in a single-component solution. In mixed solutions, conditions were identified (i) where depletion attraction was synergistically enhanced or antagonistically weakened relative to single component solutions; (ii) where the range of the depletion attraction was significantly extended and the repulsive structural force barrier was eliminated, due to simultaneous depletion of both species over different length scales; and (iii) where one species was the dominant depletant and forces in mixtures were indistinguishable from those in a single component solution of the dominant depletant.

Control of the colloidal depletion force in nonionic polymer solutions by complexation with anionic surfactants.

Hypothesis: Charge, size and concentration of depletants control the magnitude and range of depletion and structural forces. Noncovalent association of nonionic polymers with ionic surfactants may therefore synergistically enhance these forces to an extent that depends on the structure and composition of the resulting complexes.

Experiments: Forces were measured between a silica sphere and a silica plate in solutions of Pluronic F108 nonionic poly(ethylene oxide - block - propylene oxide - block - ethylene oxide) triblock copolymers and anionic sodium dodecylsulfate (SDS) surfactants using colloidal probe atomic force microscopy as a function of polymer, surfactant and NaCl background electrolyte concentrations.

Flow regime transitions and effects on solute transport in surfactant-driven Marangoni flows.

Hypothesis: Surfactant-driven Marangoni flow on liquid films is predicted to depend on subphase depth and initial surface tension difference between the subphase and deposited surfactant solution drop. Changes in flow behavior will impact transport of soluble species entrained in the Marangoni flow along the surface. In extreme cases, the subphase film may rupture, limiting transport.

Evolution and Disappearance of Solvent Drops on Miscible Polymer Subphases.

Traditionally, an interface is defined as a boundary between immiscible phases. However, previous work has shown that even when two fluids are completely miscible, they maintain a detectable "effective interface" for long times. Miscible interfaces have been studied in various systems of two fluids with a single boundary between them.