Electric fields near undulating dielectric membranes.

Dielectric interfaces are crucial to the behavior of charged membranes, from graphene to synthetic and biological lipid bilayers. Understanding electrolyte behavior near these interfaces remains a challenge, especially in the case of rough dielectric surfaces. A lack of analytical solutions consigns this problem to numerical treatments. We report an analytic method for determining electrostatic potentials near curved dielectric membranes in a two-dimensional periodic "slab" geometry using a periodic summation of Green's functions. This method is amenable to simulating arbitrary groups of charges near surfaces with two-dimensional deformations. We concentrate on one-dimensional undulations. We show that increasing membrane undulation increases the asymmetry of interfacial charge distributions due to preferential ionic repulsion from troughs. In the limit of thick membranes, we recover results mimicking those for electrolytes near a single interface. Our work demonstrates that rough surfaces generate charge patterns in electrolytes of charged molecules or mixed-valence ions.

Enhanced phoretic self-propulsion of active colloids through surface charge asymmetry.

Charged colloidal particles propel themselves through asymmetric fluxes of chemically generated ions on their surface. We show that asymmetry in the surface charge distribution provides an additional mode of self-propulsion at the nanoscale for chemically active particles that produce ionic species. Particles of sizes smaller than or comparable to the Debye length achieve directed self-propulsion through surface charge asymmetry even when ionic flux is uniform over its surface. Janus nanoparticles endowed with both surface charge and ionic flux asymmetries result in enhanced propulsion speeds of the order of µm/s or higher. Our work suggests an alternative avenue for specifying surface properties that optimize self-propulsion in ionic media.

Restructuring a passive colloidal suspension using a rotationally driven particle.

The interaction between passive and active/driven particles has introduced a new way to control colloidal suspension properties from particle aggregation to crystallization. Here, we focus on the hydrodynamic interaction between a single rotational driven particle and a suspension of passive particles near the floor. Using experiments and Stokesian dynamics simulations that account for near-field lubrication, we demonstrate that the flow induced by the driven particle can induce long-ranged rearrangement in a passive suspension. We observe an accumulation of passive particles in front of the driven particle and a depletion of passive particles behind the driven particle. This restructuring generates a pattern that can span a range more than 10 times the driven particles radius. We further show that size scale of the pattern is only a function of the particles height above the floor.

Reexpansion of charged nanoparticle assemblies in concentrated electrolytes.

Electrostatic forces in solutions are highly relevant to a variety of fields, ranging from electrochemical energy storage to biology. However, their manifestation in concentrated electrolytes is not fully understood, as exemplified by counterintuitive observations of colloidal stability and long-ranged repulsions in molten salts. Highly charged biomolecules, such as DNA, respond sensitively to ions in dilute solutions. Here, we use non-base-pairing DNA-coated nanoparticles (DNA-NP) to analyze electrostatic interactions in concentrated salt solutions. Despite their negative charge, these conjugates form colloidal crystals in solutions of sufficient divalent cation concentration. We utilize small-angle X-ray scattering (SAXS) to study such DNA-NP assemblies across the full accessible concentration ranges of aqueous CaCl2, MgCl2, and SrCl2 solutions. SAXS shows that the crystallinity and phases of the assembled structures vary with cation type. For all tested salts, the aggregates contract with added ions at low salinities and then begin expanding above a cation-dependent threshold salt concentration. Wide-angle X-ray scattering (WAXS) reveals enhanced positional correlations between ions in the solution at high salt concentrations. Complementary molecular dynamics simulations show that these ion-ion interactions reduce the favorability of dense ion configurations within the DNA brushes below that of the bulk solution. Measurements in solutions with lowered permittivity demonstrate a simultaneous increase in ion coupling and decrease in the concentration at which aggregate expansion begins, thus confirming the connection between these phenomena. Our work demonstrates that interactions between charged objects continue to evolve considerably into the high-concentration regime, where classical theories project electrostatics to be of negligible consequence.

Inhibiting the Keap1/Nrf2 Protein-Protein Interaction with Protein-Like Polymers.

Successful and selective inhibition of the cytosolic protein-protein interaction (PPI) between nuclear factor erythroid 2-related factor 2 (Nrf2) and Kelch-like ECH-associating protein 1 (Keap1) can enhance the antioxidant response, with the potential for a therapeutic effect in a range of settings including in neurodegenerative disease (ND). Small molecule inhibitors have been developed, yet many have off-target effects, or are otherwise limited by poor cellular permeability. Peptide-based strategies have also been attempted to enhance specificity, yet face challenges due to susceptibility to degradation and lack of cellular penetration. Herein, these barriers are overcome utilizing a polymer-based proteomimetics. The protein-like polymer (PLP) consists of a synthetic, lipophilic polymer backbone displaying water soluble Keap1-binding peptides on each monomer unit forming a brush polymer architecture. The PLPs are capable of engaging Keap1 and displacing the cellular protective transcription factor Nrf2, which then translocates to the nucleus, activating the antioxidant response element (ARE). PLPs exhibit increased Keap1 binding affinity by several orders of magnitude compared to free peptides, maintain serum stability, are cell-penetrant, and selectively activate the ARE pathway in cells, including in primary cortical neuronal cultures. Keap1/Nrf2-inhibitory PLPs have the potential to impact the treatment of disease states associated with dysregulation of oxidative stress, such as NDs.

Transformations in crystals of DNA-functionalized nanoparticles by electrolytes.

Colloidal crystals have applications in water treatments, including water purification and desalination technologies. It is, therefore, important to understand the interactions between colloids as a function of electrolyte concentration. We study the assembly of DNA-grafted gold nanoparticles immersed in concentrated electrolyte solutions. Increasing the concentration of divalent Ca2+ ions leads to the condensation of nanoparticles into face-centered-cubic (FCC) crystals at low electrolyte concentrations. As the electrolyte concentration increases, the system undergoes a phase change to body-centered-cubic (BCC) crystals. This phase change occurs as the interparticle distance decreases. Molecular dynamics analysis suggests that the interparticle interactions change from strongly repulsive to short-range attractive as the divalent-electrolyte concentration increases. A thermodynamic analysis suggests that increasing the salt concentration leads to significant dehydration of the nanoparticle environment. We conjecture that the intercolloid attractive interactions and dehydrated states favour the BCC structure. Our results gain insight into salting out of colloids such as proteins as the concentration of salt increases in the solution.

Kinetic Growth of Multicomponent Microcompartment Shells.

An important goal of systems and synthetic biology is to produce high value chemical species in large quantities. Microcompartments, which are protein nanoshells encapsulating catalytic enzyme cargo, could potentially function as tunable nanobioreactors inside and outside cells to generate these high value species. Modifying the morphology of microcompartments through genetic engineering of shell proteins is one viable strategy to tune cofactor and metabolite access to encapsulated enzymes. However, this is a difficult task without understanding how changing interactions between the many different types of shell proteins and enzymes affect microcompartment assembly and shape. Here, we use multiscale molecular dynamics and experimental data to describe assembly pathways available to microcompartments composed of multiple types of shell proteins with varied interactions. As the average interaction between the enzyme cargo and the multiple types of shell proteins is weakened, the shell assembly pathway transitions from (i) nucleating on the enzyme cargo to (ii) nucleating in the bulk and then binding the cargo as it grows to (iii) an empty shell. Atomistic simulations and experiments using the 1,2-propanediol utilization microcompartment system demonstrate that shell protein interactions are highly varied and consistent with our multicomponent, coarse-grained model. Furthermore, our results suggest that intrinsic bending angles control the size of these microcompartments. Overall, our simulations and experiments provide guidance to control microcomparmtent size and assembly by modulating the interactions between shell proteins.

Janus magnetoelastic membrane swimmers.

Soft swimming microrobots have attracted considerable attention due to their potential applications in diverse fields ranging from biomedicines to environmental remediation. The locomotion control is of importance to the research of micromachines and microrobots. Inspired by the motility strategies of living microorganisms, such as flagella, cilia, and euglenoids, we focus on propulsion mechanisms with a design of Janus magnetoelastic crystalline membrane microswimmers actuated by time-varying magnetic fields. Such a Janus swimmer consists of a ferromagnetic cap completed by a magnetoelastic membrane body, where superparamagnetic particles are uniformly distributed on the surface. Under the influence of external magnetic fields, the swimmer undergoes complex shape transitions due to the interplay between the magnetic dipole-dipole interactions, the elasticity of the magnetoelastic membranes, and also the hydrodynamics of surrounding fluids. We show that those shape changes are nonreciprocal, which can generate locomotion such that the propulsion speed can be optimized by tailoring the membrane elastic properties. Besides, we also demonstrate that the Janus swimmer can be magnetically guided in a spiral trajectory. With such adequate control of locomotion in both speed and direction via non-invasive magnetic fields, this study provides another promising candidate design for the future development of microswimmers.

Surface polarization enhances ionic transport and correlations in electrolyte solutions nanoconfined by conductors.

Layered materials that perform mixed electron and ion transport are promising for energy harvesting, water desalination, and bioinspired functionalities. These functionalities depend on the interaction between ionic and electronic charges on the surface of materials. Here we investigate ion transport by an external electric field in an electrolyte solution confined in slit-like channels formed by two surfaces separated by distances that fit only a few water layers. We study different electrolyte solutions containing monovalent, divalent, and trivalent cations, and we consider walls made of non-polarizable surfaces and conductors. We show that considering the surface polarization of the confining surfaces can result in a significant increase in ionic conduction. The ionic conductivity is increased because the conductors' screening of electrostatic interactions enhances ionic correlations, leading to faster collective transport within the slit. While important, the change in water's dielectric constant in confinement is not enough to explain the enhancement of ion transport in polarizable slit-like channels.

Tailoring Interactions of Random Copolymer Polyelectrolyte Complexes to Remove Nanoplastic Contaminants from Water.

We investigate the usage of polyelectrolyte complex materials for water remediation purposes, specifically their ability to remove nanoplastics from water, on which there is currently little to no prior research. We demonstrate that oppositely charged random copolymers are effective at quantitatively removing nanoplastic contamination from aqueous solution. The mechanisms underlying this remediation ability are explored through computational simulations, with corroborating quartz crystal microbalance adsorption experiments. We find that hydrophobic nanostructures and interactions likely play an important role.

Field-driven cluster formation in two-dimensional colloidal binary mixtures.

We study size- and charge-asymmetric oppositely charged colloids driven by an external electric field. The large particles are connected by harmonic springs, forming a hexagonal-lattice network, while the small particles are free of bonds and exhibit fluidlike motion. We show that this model exhibits a cluster formation pattern when the external driving force exceeds a critical value. The clustering is accompanied with stable wave packets in vibrational motions of the large particles.

Colloidal superionic conductors.

Nanoparticles with highly asymmetric sizes and charges that self-assemble into crystals via electrostatics may exhibit behaviors reminiscent of those of metals or superionic materials. Here, we use coarse-grained molecular simulations with underdamped Langevin dynamics to explore how a binary charged colloidal crystal reacts to an external electric field. As the field strength increases, we find transitions from insulator (ionic state), to superionic (conductive state), to laning, to complete melting (liquid state). In the superionic state, the resistivity decreases with increasing temperature, which is contrary to metals, yet the increment decreases as the electric field becomes stronger. Additionally, we verify that the dissipation of the system and the fluctuation of charge currents obey recently developed thermodynamic uncertainty relation. Our results describe charge transport mechanisms in colloidal superionic conductors.

Positional ordering induced by dynamic steric interactions in superparamagnetic rods.

The dynamic motion produced by precessing magnetic fields can drive matter into far-from-equilibrium states. We predict 1D periodic ordering in systems of precessing rods when magnetic interactions between rods remain insignificant. The precession angle of the rods is completely determined by the field's precession angle and the ratio of the field's precession frequency and the characteristic response frequency of the rods. We develop a molecular dynamics model that explicitly calculates magnetic interactions between particles, and we also simulate rods in the limit of a strong and fast precessing magnetic field where inter-rod magnetic interactions are negligible, using a purely steric model. Our simulations show how steric interactions drive the rods from a positionally disordered phase (nematic) to a layered (smectic) phase. As the rod precession angle increases, the nematic-smectic transition density significantly decreases. The minimization of unfavorable steric interactions also induces phase separation in binary mixtures of rods of different lengths. This effect is general to any force that produces precession in elongated particles. This work will advance the understanding and control of out-of-equilibrium soft matter systems.