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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. [ABSTRACT FROM AUTHOR]

Understanding electrostatic interactions among dielectric bodies in the atmosphere and aerosols is central to controlling their aggregation. Polarization effects, which are frequently ignored, are crucial to determine interactions when geometrical anisotropies are present due to surface-induced charge segregation. Here, we adopt a direct integral formulation that accounts for the problem of charged dielectric bodies immersed in a continuum media to explore particle aggregation via geometrical tuning. We show that by breaking the structural symmetry and modifying the close-contact surface between particles of equal charge, it is possible to obtain attractive regimes at short and long distances. We evaluate the electrostatic forces and energy of a set of dimers and trimers composed of spheres, oblates, and prolates in a vacuum, where no counter-ions are present, to construct a phase diagram with the conditions required to form stable aggregates as a function of the geometrical anisotropy. We found that it is possible to direct the aggregation (or dispersion) of two and three positive dielectric particles by adjusting their geometry and controlling the contact surface among them. Our results give insight into a way to control the aggregation of dielectric systems and offer a prospect for directing the assembly of complex particle structures. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Mesoscopic clusters composed of oppositely charged particles are ubiquitous in synthetic and biological soft materials. The effective interaction between these clusters is influenced by their polarizability, that is, the ability of their constituent charges to re-arrange in response to an external electrical field. Here, using coarse-grained simulations, we show that the polarizability of electrically neutral ionic clusters decreases as the number of constituent charges increases and/or their Coulombic interaction strength increases for various ion valencies, ion densities, and degrees of cluster boundary hardness. For clusters of random ionomers and their counterions, their polarizability is shown to depend on the number of polymer chains. The variation of the cluster polarizability with the cluster size indicates that throughout the assembly, the induced-dipole interactions between the clusters may be reduced substantially as they acquire more charges while maintaining zero net charge. Under certain conditions, the induced-dipole interactions may become repulsive, as inferred from our simulations with a polarizable solvent. As a result, the dipole-induced related interactions can serve as a counterbalancing force that contributes to the self-limiting aggregation of charge-containing assemblies. [ABSTRACT FROM AUTHOR]

In solid–liquid, or liquid–liquid, interfaces with dielectric contrast, charged particles interact with the induced polarization charge of the interface. These interactions contribute to an effective self-energy of the bulk ions and mediate ion–ion interactions. For flat interfaces, the self-energy and the mediated interactions are neatly constructed by the image charge method. For other geometries, explicit results are scarce and the problem must be treated via approximations or direct computation. The case of interfaces with roughness is of great practical importance. This article provides analytical results, valid to first-order in perturbation theory, for the self-energy of particles near rough substrates. Explicit formulas are provided for the case of a sinusoidal deformation of a flat surface. Generic deformations can be treated by superposition. In addition to results for the self-energy, the surface polarization charge is presented as a quadrature. The interaction between an ion and the deformed surface is modified by the change in relative distance as well as by the local curvature of the surface. Solid walls, with a lower dielectric constant than the liquid, repel all ions. We show that the repulsion is reduced by local convexity and enhanced by concavity; dimples are more repulsive than pimples. [ABSTRACT FROM AUTHOR]

The transport of polyelectrolytes confined by oppositely charged surfaces and driven by a constant electric field is of interest in studies of DNA separation according to size. Using molecular dynamics simulations that include the surface polarization effect, we find that the mobilities of the polyelectrolytes and their counterions change non-monotonically with the confinement surface charge density. For an optimum value of the confinement charge density, efficient separation of polyelectrolytes can be achieved over a wide range of polyelectrolyte charge due to the differential friction imparted by oppositely charged confinement on the polyelectrolyte chains. Furthermore, by altering the placement of the charged confinement counterions, enhanced polyelectrolyte separation can be achieved by utilizing the surface polarization effect due to dielectric mismatch between the media inside and outside the confinement. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The ion distribution of electrolytes near interfaces with dielectric contrast has important consequences for electrochemical processes and many other applications. To date, most studies of such systems have focused on geometrically simple interfaces, for which dielectric effects are analytically solvable or computationally tractable. However, all real surfaces display nontrivial structure at the nanoscale and have, in particular, a nonuniform local curvature. Using a recently developed, highly efficient computational method, we investigate the effect of surface geometry on ion distribution and interface polarization. We consider an asymmetric 2:1 electrolyte bounded by a sinusoidally deformed solid surface. We demonstrate that even when the surface is neutral, the electrolyte acquires a nonuniform ion density profile near the surface. This profile is asymmetric and leads to an effective charging of the surface. We furthermore show that the induced charge is modulated by the local curvature. The effective charge is opposite in sign to the multivalent ions and is larger in concave regions of the surface. [ABSTRACT FROM AUTHOR]

Odd viscosity is associated with a number of striking physical phenomena: a disk rotating in a viscous liquid experiences a normal compressive or tensile stress depending on its sense of rotation; chiral active matter interfacial deformations level off in a manner akin to surface tension; and unstable thermocapillary films become stabilized. In this article we show that odd viscosity decreases the size and intensity of Moffatt vortices in a corner formed by a solid substrate and a free interface. The effect is present because odd viscosity creates a normal-stress-induced shear stress at the liquid–gas interface. The new shear stress is out of phase and oppositely directed with respect to the interfacial liquid velocity. It squeezes the vortices and damps their rotation. As a consequence, Moffatt vortices can now be observed with greater facility in an experiment. Odd viscosity also increases the range of corner angles over which Moffatt vortices can be observed, and, in general, it shows a tendency to moderate singular behaviour. [ABSTRACT FROM AUTHOR]

Engineering subcellular organization in microbes shows great promise in addressing bottlenecks in metabolic engineering efforts; however, rules guiding selection of an organization strategy or platform are lacking. Here, we study compartment morphology as a factor in mediating encapsulated pathway performance. Using the 1,2-propanediol utilization microcompartment (Pdu MCP) system from Salmonella enterica serovar Typhimurium LT2, we find that we can shift the morphology of this protein nanoreactor from polyhedral to tubular by removing vertex protein PduN. Analysis of the metabolic function between these Pdu microtubes (MTs) shows that they provide a diffusional barrier capable of shielding the cytosol from a toxic pathway intermediate, similar to native MCPs. However, kinetic modeling suggests that the different surface area to volume ratios of MCP and MT structures alters encapsulated pathway performance. Finally, we report a microscopy-based assay that permits rapid assessment of Pdu MT formation to enable future engineering efforts on these structures. Morphology of metabolosomes affects the encapsulated pathway performance. Here, the authors combine experimental characterizations with structural and kinetic modeling to reveal how the shell protein PduN changes the morphology of 1,2-propanediol utilization (Pdu) metabolosome and how this morphology shift impacts Pdu function. [ABSTRACT FROM AUTHOR]

In biological and synthetic materials, many important processes involve charges that are present in a medium with spatially varying dielectric permittivity. To accurately understand the role of electrostatic interactions in such systems, it is important to take into account the spatial dependence of the permittivity of the medium. However, due to the ensuing theoretical and computational challenges, this inhomogeneous dielectric response of the medium is often ignored or excessively simplified. We develop a variational formulation of electrostatics to accurately investigate systems that exhibit this inhomogeneous dielectric response. Our formulation is based on a true energy functional of the polarization charge density. The defining characteristic of a true energy functional is that at its minimum it evaluates to the actual value of the energy; this is a feature not found in many commonly used electrostatic functionals. We explore in detail the charged systems that exhibit sharp discontinuous change in dielectric permittivity, and we show that for this case our functional reduces to a functional of only the surface polarization charge density. We apply this reduced functional to study model problems for which analytical solutions are well known. We demonstrate, in addition, that the functional has many properties that make it ideal for use in molecular dynamics simulations. [ABSTRACT FROM AUTHOR]

Understanding nanoscale interactions at the interface between two media with different dielectric constants is crucial for controlling many environmental and biological processes, and for improving the efficiency of energy storage devices. In this contributed paper, we show that polarization effects due to such dielectric mismatch remarkably influence the double-layer structure of a polyelectrolyte solution confined between two charged surfaces. Surprisingly, the electrostatic potential across the adsorbed polyelectrolyte double layer at the confining surface is found to decrease with increasing surface charge density, indicative of a negative differential capacitance. Furthermore, in the presence of polarization effects, the electrostatic energy stored in the double-layer structure is enhanced with an increase in the charge amplification, which is the absorption of ions on a like-charged surface. We also find that all of the important double-layer properties, such as charge amplification, energy storage, and differential capacitance, strongly depend on the polyelectrolyte backbone flexibility and the solvent quality. These interesting behaviors are attributed to the interplay between the conformational entropy of the confined polyelectrolytes, the Coulombic interaction between the charged species, and the repulsion from the surfaces with lower dielectric constant. [ABSTRACT FROM AUTHOR]

Hybrid systems based on covalent polymers and supramolecular assemblies offer unique opportunities for functional materials based on the pathway-dependent dynamic structures of supramolecular assemblies and the mechanical stability of covalent polymers. We report here on the synthesis of functional hybrid hydrogels containing self-assembling chromophore amphiphiles and polyelectrolytes. Chromophore amphiphiles were introduced into non-aqueous solvent swollen polymer matrices and self-assembly of the chromophore amphiphiles into crystalline nanostructures was triggered in the confined environment of the covalent network upon solvent exchange for water. Opposite charges in the covalent polyelectrolyte and the chromophore amphiphiles and sterics entrap the supramolecular assemblies within the mechanically stable network. However, molecular components necessary for catalysis, byproducts from photocatalysis, and the hydrogen produced are able to diffuse in or out of the covalent network to create a reusable robust host for photocatalysis. By varying the monomer and crosslinker composition in the feed, we can tune the porosity of the network as well as the chemical environment in which supramolecular crystallization of the chromophore amphiphiles takes place. This allows optimization of the hydrogel mechanical properties, retention of the chromophore amphiphile assemblies, and the photocatalytic reaction efficiency. Coarse-grained molecular dynamics simulations revealed that the chromophore amphiphile assembly is guided by the polyelectrolyte network via ionic interactions. We also demonstrate successful photocatalytic hydrogen production from catalyst-laden hybrid hydrogels with the turnover frequency approaching that of the supramolecular hydrogel system, and also show that the hybrid hydrogels can be reused over multiple cycles as photosensitizers. [ABSTRACT FROM AUTHOR]

Bilayers of amphiphiles can organize into spherical vesicles, nanotubes, planar, undulating, and helical nanoribbons, and scroll-like cochleates. These bilayer-related architectures interconvert under suitable conditions. Here, a charged, chiral amphiphile (palmitoyl-lysine, C16-K1) is used to elucidate the pathway for planar nanoribbon to cochleate transition induced by salt (NaCl) concentration. In situ small- and wide-angle X-ray scattering (SAXS/WAXS), atomic force and cryogenic transmission electron microscopies (AFM and cryo-TEM) tracked these transformations over angstrom to micrometer length scales. AFM reveals that the large length (L) to width (W) ratio nanoribbons (L/W > 10) convert to sheets (L/W → 1) before rolling into cochleates. A theoretical model based on electrostatic and surface energies shows that the nanoribbons convert to sheets via a first-order transition, at a critical Debye length, with 2 shallow minima of the order of thermal energy at L/W >> 1 and at L/W = 1. SAXS shows that interbilayer spacing (D) in the cochleates scales linearly with the Debye length, and ranges from 13 to 35 nm for NaCl concentrations from 100 to 5 mM. Theoretical arguments that include electrostatic and elastic energies explain the membrane rolling and the bilayer separation-Debye length relationship. These models suggest that the salt-induced ribbon to cochleate transition should be common to all charged bilayers possessing an intrinsic curvature, which in the present case originates from molecular chirality. Our studies show how electrostatic interactions can be tuned to attain and control cochleate structures, which have potential for encapsulating, and releasing macromolecules in a size-selective manner. [ABSTRACT FROM AUTHOR]

By combining molecular dynamics simulations and analytical arguments, we investigate the elastic properties of charged lipid bilayers. We show that electrostatic interactions between the head groups can lead to solidification of the lipid bilayer that would otherwise be in a liquid state if the charges were absent. All elastic parameters of the bilayer such as the bending rigidity κ and the two-dimensional bulk modulus λ and Young's modulus Y are found to depend on the values of the charges assigned to the lipid head groups. To extract κ and λ, we fit the molecular dynamics data to a standard elastic model for lipid bilayers. Moreover, we analytically obtain the dependence of the Young modulus Y on the relative strengths of electrostatic and van der Waals interactions in the zero temperature limit. [ABSTRACT FROM AUTHOR]

Motivated by recent experimental findings, we present here a minimal analytical model illustrating that the steric interactions among the ionic components can provide a simple, generic mechanism for like-charge crystallization in prototypical nanoparticle systems with counterions in polar solvents. In particular, the underlying steric interactions among these ionic components arise from the structural organization of the polar solvent molecules surrounding these ions as molecular dipole moments that may cooperatively enhance or counteract existing entropic depletion and electrostatic forces. Phenomenologically capturing these steric effects, we assume only the existence of a short-range pairwise Gaussian interaction, which has already been employed usefully for nanoparticles with hydrophillic surfaces or grafted-polymer coatings, among these ionic components (nanoparticles and counterions). The corresponding Gaussian interaction parameters characterize tunable interaction strengths. Making use of an analytically obtained effective pairwise potential between two nanoparticles, upon the contraction of counterions, we derive phase diagrams for nanoparticle systems of varying charge- and size-ratios as a function of particle densities, and observe crystallization for a range of parameters. We further demonstrate that our minimal model is compatible with the phenomenon of charge asymmetry. [ABSTRACT FROM AUTHOR]

We investigate the equilibrium properties and the underlying dynamics of emulsions formed in asymmetric A-B copolymers in matrices of immiscible B and C molecular fluids using coarse-grained molecular dynamics simulations. The emulsions are generated by introducing net attractions among the A units of the copolymers and the C molecules. They coexist with an absorbed copolymer monolayer. We determine the interfacial properties as the emulsions are forming. In general, highly asymmetric copolymers self-assemble within the B-matrix phase into swollen micelles; the cores of which are composed of C-component material. Less asymmetric copolymers, however, after initially budding and eventually fissioning from the interfacial copolymer monolayer, generate emulsified “inverse swollen micelles” within the C-matrix phase. These stable inverse (crew-cut) swollen micelles, which form under the inward bending of the saturated or oversaturated interfaces toward the longer B-block due to the attraction between the A and C units, can encapsulate large amounts of B-matrix component in their cores. This monolayer collapse mechanism can be exploited to generate nanoreactors or containers that enhance the delivery of molecular components into immiscible molecular fluid environments. [ABSTRACT FROM AUTHOR]

The swelling of polyelectrolyte (PE) gels by 1:1 and 2:1 salts is studied via osmotic ensemble Monte Carlo simulations at constant osmotic pressure and electrolyte chemical potential of a reservoir phase in equilibrium with a model PE network. Large molecular weight gels exhibit a remarkable swelling response to small changes in 2:1 salt concentration. Gel collapse is accompanied by the formation of a previously unknown heterogeneous nanostructure, predicted by theory and observed in simulations, consisting of regions dense in monomers coexisting with regions rich in mono- and divalent ions. [ABSTRACT FROM AUTHOR]

We study the equilibrium thermodynamics between two ternary ionic systems in immiscible solvents characterized by different dielectric constants. We consider system geometries wherein the two phases of immiscible solvents occupy, respectively, semi-infinite regions of space separated by neutral and charged planar interfaces. Specifically we analyze the case where the ternary system is composed of a pair of symmetric ions plus a minority charged component of high valence. We describe the system by means of a nonlinear mean-field theory. We first obtain exact analytical solutions for the electrostatic potentials, as well as density profiles for a symmetric binary system, and then extend these results to the ternary case using the perturbation theory. We show that the corresponding adsorption and depletion of multivalent macroions at the interface are highly enhanced when compared with the monovalent case. [ABSTRACT FROM AUTHOR]

The structure of soft matter systems at interfaces is of utmost importance in the fields of nanopatterning and self-assembly. It has been shown that lamellar and hexagonal patterns can form on interfaces, for a wide variety of systems. The asphericity of charged domains is considered here for different strengths of the electrostatics, determined by the interface media, relative to the short range van der Waals interactions between the molecular components. The phase behavior of the surface structure is explored by using molecular dynamics simulations, including some dynamical aspects of the interaction between neighboring domains, using the Lindemann criterion [F. Lindemann, Z. Phys. 11, 609 (1910)]. The charge ratio of the electrostatic components influences the shape of the domains, as well as the degree of local order in the interdomain structure. [ABSTRACT FROM AUTHOR]

Light-sensitive particles have been shown to stratify in solution in a way that changes the colour of the whole suspension. The system forms a colour-changing ink that could make electronic paper a viable technology.Mixtures of light-sensitive particles reorganize to change colour. [ABSTRACT FROM AUTHOR]

Superparamagnetic nanoparticles incorporated into elastic media offer the possibility of creating actuators driven by external fields in a multitude of environments. Here, magnetoelastic membranes are studied through a combination of continuum mechanics and molecular dynamics simulations. We show how induced magnetic interactions affect the buckling and the configuration of magnetoelastic membranes in rapidly precessing magnetic fields. The field, in competition with the bending and stretching of the membrane, transmits forces and torques that drives the membrane to expand, contract, or twist. We identify critical field values that induce spontaneous symmetry breaking as well as field regimes where multiple membrane configurations may be observed. Our insights into buckling mechanisms provide the bases to develop soft, autonomous robotic systems that can be used at micro- and macroscopic length scales. [ABSTRACT FROM AUTHOR]

The microphase separation transition for asymmetric triblock and (A–B)m star copolymer melts is investigated following a mean-field approach proposed by Leibler for diblock copolymer melts. Continuous transitions are found in all triblock architectures and in stars for any m at some composition fc. The phase diagram for the equilibrium morphologies is notably altered by varying the architecture of triblock copolymers. [ABSTRACT FROM AUTHOR]

Membraneless organelles are aggregates of disordered proteins that form spontaneously to promote specific cellular functions in vivo. The possibility of synthesizing membraneless organelles out of cells will therefore enable fabrication of protein-based materials with functions inherent to biological matter. Since random copolymers contain various compositions and sequences of solvophobic and solvophilic groups, they are expected to function in nonbiological media similarly to a set of disordered proteins in membraneless organelles. Interestingly, the internal environment of these organelles has been noted to behave more like an organic solvent than like water. Therefore, an adsorbed layer of random copolymers that mimics the function of disordered proteins could, in principle, protect and enhance the proteins' enzymatic activity even in organic solvents, which are ideal when the products and/or the reactants have limited solubility in aqueous media. Here, we demonstrate via multiscale simulations that random copolymers efficiently incorporate proteins into different solvents with the potential to optimize their enzymatic activity. We investigate the key factors that govern the ability of random copolymers to encapsulate proteins, including the adsorption energy, copolymer average composition, and solvent selectivity. The adsorbed polymer chains have remarkably similar sequences, indicating that the proteins are able to select certain sequences that best reduce their exposure to the solvent. We also find that the protein surface coverage decreases when the fluctuation in the average distance between the protein adsorption sites increases. The results herein set the stage for computational design of random copolymers for stabilizing and delivering proteins across multiple media. [ABSTRACT FROM AUTHOR]

Skeletal muscle provides inspiration on how to achieve reversible, macroscopic, anisotropic motion in soft materials. Here we report on the bottom-up design of macroscopic tubes that exhibit anisotropic actuation driven by a thermal stimulus. The tube is built from a hydrogel in which extremely long supramolecular nanofibers are aligned using weak shear forces, followed by radial growth of thermoresponsive polymers from their surfaces. The hierarchically ordered tube exhibits reversible anisotropic actuation with changes in temperature, with much greater contraction perpendicular to the direction of nanofiber alignment. We identify two critical factors for the anisotropic actuation, macroscopic alignment of the supramolecular scaffold and its covalent bonding to polymer chains. Using finite element analysis and molecular calculations, we conclude polymer chain confinement and mechanical reinforcement by rigid supramolecular nanofibers are responsible for the anisotropic actuation. The work reported suggests strategies to create soft active matter with molecularly encoded capacity to perform complex tasks. [ABSTRACT FROM AUTHOR]

ABSTRACT: Cantilever‐free scanning probe lithography (SPL) employs soft elastomeric pen arrays to deliver material or energy to a surface to achieve a high‐resolution, high‐throughput, and low‐cost nanopatterning. In particular, microscale elastomeric pyramid pen arrays are often adopted as the cantilever‐free architecture owing to their distinct structural and mechanical properties. To better understand the mechanical behavior of the elastomeric pyramid pen array during the lithographic printing process, we numerically investigate the compression of an elastomeric pyramid array in a nonadhesive and frictionless contact with a rigid substrate. Simple scaling laws of the width of the contact surface with respect to the compression displacement and force are found and compared with previous models and experiments. By changing the interpyramid distance or the thickness of the base of the pyramid array, increasing deviations from the established scaling laws are observed and explained. Furthermore, we demonstrate that the unique morphology of a compressed pyramid primarily determines the unusual shape of the features fabricated by a specific cantilever‐free SPL technique. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 731–738 [ABSTRACT FROM AUTHOR]

Controlling interactions between proteins and nanoparticles in electrolyte solutions is crucial for advancing biological sciences and biotechnology. The assembly of charged nanoparticles (NPs) and proteins in aqueous solutions can be directed by modifying the salt concentration. High concentrations of monovalent salt can induce the solubilization or crystallization of NPs and proteins. By using a multiscale coarse-grained molecular dynamics approach, we show that, due to ionic correlations in the electrolyte, NPs pairs at high monovalent salt concentrations interact via remarkably strong long-range attractions or repulsions, which can be split into three regimes depending on the surface charge densities of the NPs. NPs with zero-to-low surface charge densities interact via a long-range attraction that is stronger and has a similar range to the depletion attraction induced by polymers with radius of gyrations comparable to the NP diameter. On the other hand, moderately charged NPs with smooth surfaces as well as DNA-functionalized NPs with no possibility of hybridization between them interact via a strong repulsion of range and strength larger than the repulsion predicted by models that neglect ionic correlations, including the Derjaguin-Landau-Vervey-Overbeek (DLVO) model. Interactions between strongly charged NPs (>2 e/nm²), both types smooth and DNA-functionalized NPs, show an attractive potential well at intermediate-to-high salt concentrations, which demonstrates that electrolytes can induce aggregation of strongly charged NPs. Our work provides an improved understanding of the role of ionic correlations in NP assembly and design rules to utilize the salting-out process to crystallize NPs. [ABSTRACT FROM AUTHOR]

Directed crystallization of a large variety of nanoparticles, including proteins, via DNA hybridization kinetics has led to unique materials with a broad range of crystal symmetries. The nanoparticles are functionalized with DNA chains that link neighboring functionalized units. The shape of the nanoparticle, the DNA length, the sequence of the hybridizing DNA linker, and the grafting density determine the crystal symmetries and lattice spacing. By carefully selecting these parameters, one can, in principle, achieve all the symmetries found for both atomic and colloidal crystals of asymmetric shapes as well as new symmetries and can drive transitions between them. A scale-accurate coarse-grained model with explicit DNA chains provides the design parameters, including the degree of hybridization, to achieve specific crystal structures. The model also provides surface energy values to determine the shape of defect-free single crystals with macroscopic anisotropic properties, which has potential for the fabrication of materials with specific optical and mechanical properties. [ABSTRACT FROM AUTHOR]

ABSTRACT Self-assembled peptide amphiphile (PA) nanofibers are a class of supramolecular materials with promising applications in nanotechnology. Alignment of nanofibers, which is essential for biomaterials applications, is achieved at low salt concentrations in the PA nanofiber suspensions. Regardless of its importance, the effect of ion concentration on the properties of these nanostructures remains unexplored. Using atomistic molecular dynamics simulations, canonical PA nanostructures are investigated to elucidate the relationship between counterion condensation and morphological changes. Simulations reveal that nanofibers with the highest cross-section density have expanded radii. This expansion decreases the accessible volume for sodium counterions and diminishes the counterion translational entropy, while also reducing the total electrostatic potential. Interestingly, we show that the competition between these effects leads to a fraction of condensed counterions independent of the fiber radius. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 901-906 [ABSTRACT FROM AUTHOR]

A perversion in an otherwise uniform helical structure, such as a climbing plant tendril, refers to a kink that connects two helices with opposite chiralities. Such singularity structures are widely seen in natural and artificial mechanical systems, and they provide the fundamental mechanism of helical symmetry breaking. However, it is still not clear how perversions arise in various helical structures and which universal principles govern them. As such, a heterogeneous elastic bistrip system provides an excellent model to address these questions. Here, we investigate intrinsic perversion properties which are independent of strip shapes. This study reveals the rich physics of perversions in the 3D elastic system, including the condensation of strain energy over perversions during their formation, the repulsive nature of the perversion–perversion interaction, and the coalescence of perversions that finally leads to a linear defect structure. This study may have implications for understanding relevant biological motifs and for use of perversions as energy storers in the design of micromuscles and soft robotics. [ABSTRACT FROM AUTHOR]

The lanthanide contraction is conceptualized traditionally through coordination chemistry. Here we break this mold in a structural study of lanthanide ions dissolved in an amphiphilic liquid. The lanthanide contraction perturbs the weak interactions between molecular aggregates that drive mesoscale assembly and emergent behavior. The weak interactions correlate with lanthanide ion transport properties, suggesting new strategies for rare-earth separation that exploit forces outside of the coordination sphere. [ABSTRACT FROM AUTHOR]

The stability of colloidal suspensions is crucial in a wide variety of processes, including the fabrication of photonic materials and scaffolds for biological assemblies. The ionic strength of the electrolyte that suspends charged colloids is widely used to control the physical properties of colloidal suspensions. The extensively used two-body Derjaguin-Landau-Verwey-Overbeek (DLVO) approach allows for a quantitative analysis of the effective electrostatic forces between colloidal particles. DLVO relates the ionic double layers, which enclose the particles, to their effective electrostatic repulsion. Nevertheless, the double layer is distorted at high macroion volume fractions. Therefore, DLVO cannot describe the many-body effects that arise in concentrated suspensions. We show that this problem can be largely resolved by identifying effective point charges for the macroions using cell theory. This extrapolated point charge (EPC) method assigns effective point charges in a consistent way, taking into account the excluded volume of highly charged macroions at any concentration, and thereby naturally accounting for high volume fractions in both salt-free and added-salt conditions. We provide an analytical expression for the effective pair potential and validate the EPC method by comparing molecular dynamics simulations of macroions and monovalent microions that interact via Coulombic potentials to simulations of macroions interacting via the derived EPC effective potential. The simulations reproduce the macroion-macroion spatial correlation and the virial pressure obtained with the EPC model. Our findings provide a route to relate the physical properties such as pressure in systems of screened Coulomb particles to experimental measurements. [ABSTRACT FROM AUTHOR]