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Active components incorporated in materials generate motion by inducing conformational changes in response to external fields. Magnetic fields are particularly interesting as they can actuate materials remotely. Millimeter-sized ferrofluid droplets placed on a solid surface, surrounded by an ambient gas phase, are shown here to migrate under a rotating magnetic field due to the periodic deformation of the liquid-gas interface. This interface wobbling leads to droplet migration with speeds that increase as the amplitude and frequency of the magnetic field increase. In addition to migrating in a controlled manner, we demonstrate the ability of magnetic droplets to clean surface impurities and transport cargo.

Peptide surfactants (PEPS) are studied to capture and retain rare earth elements (REEs) at air-water interfaces to enable REE separations. Peptide sequences, designed to selectively bind REEs, depend crucially on the position of ligands within their binding loop domain. These ligands form a coordination sphere that wraps and retains the cation. We study variants of lanthanide binding tags (LBTs) designed to complex strongly with Tb$^{3+}$. The peptide LBT$^{5-}$ (with net charge -5) is known to bind Tb$^{3+}$ and adsorb with more REE cations than peptide molecules, suggesting that undesired non-specific Coulombic interactions occur. Rheological characterization of interfaces of LBT$^{5-}$ and Tb$^{3+}$ solutions reveal the formation of an interfacial gel. To probe whether this gelation reflects chelation among intact adsorbed LBT$^{5-}$:Tb$^{3+}$ complexes or destruction of the binding loop, we study a variant, LBT$^{3-}$, designed to form net neutral LBT$^{3-}$:Tb$^{3+}$ complexes. Solutions of LBT$^{3-}$ and Tb$^{3+}$ form purely viscous layers in the presence of excess Tb$^{3+}$, indicating that each peptide binds a single REE in an intact coordination sphere. We introduce the variant RR-LBT$^{3-}$ with net charge -3 and anionic ligands outside of the coordination sphere. We find that such exposed ligands promote interfacial gelation. Thus, a nuanced requirement for interfacial selectivity of PEPS is proposed: that anionic ligands outside of the coordination sphere must be avoided to prevent the non-selective recruitment of REE cations. This view is supported by simulation, including interfacial molecular dynamics simulations, and interfacial metadynamics simulations of the free energy landscape of the binding loop conformational space.

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 of the driven particle's radius. We further show that size scale of the pattern is only a function of the particle's height above the floor., Comment: S.-Y.C. and H.L-R. contributed equally

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., Comment: Main article: 25 pages, 6 figures; Supplementary Material: 5 pages, 5 figures

Acid-base equilibria directly influence the functionality and behavior of particles in a system. Due to the ionizing effects of acid-base functional groups, particles will undergo charge exchange. The degree of ionization and their intermolecular and electrostatic interactions are controlled by varying the pH and salt concentration of the solution in a system. Although the pH can be tuned in experiments, it is hard to model this effect using simulations or theoretical approaches. This is due to the difficulty in treating charge regulation and capturing the cooperative effects in a colloidal suspension with Coulombic interaction. In this work, we analyze a suspension of ionizable colloidal particles via Brownian simulations and derive a phase diagram of the system as a function of pH. It is observed that as pH increases, particles functionalized with acid groups change their arrangement from face-centered cubic (FCC) packing to a disordered state. We attribute these transitions to an increase in the degree of charge polydispersity arising from an increase in pH. Our work shows that charge regulation leads to amorphous solids in colloids when the mean nanoparticle charge is sufficiently high., Comment: 15 pages, 12 Figures

PyMembrane is a software package for simulating liquid and elastic membranes using a discretisation of the continuum description based on unstructured triangulated two-dimensional meshes embedded in three-dimensional space. The package is written in C++, with a flexible and intuitive Python interface, allowing for a quick setup, execution and analysis of complex simulations. PyMembrane follows modern software engineering principles and features a modular design that allows for straightforward implementation of custom extensions while ensuring consistency and enabling inexpensive maintenance. A hallmark feature of this design is the use of a standardized C++ interface which streamlines adding new functionalities. Furthermore, PyMembrane uses data structures optimised for unstructured meshes, ensuring efficient mesh operations and force calculations. By providing several templates for typical simulations supplemented by extensive documentation, the users can seamlessly set up and run research-level simulations and extend the package to integrate additional features, underscoring PyMembrane's commitment to user-centric design., Comment: 7 Figures

Recent findings suggest that shell protein distribution and morphology of bacterial microcompartments regulate the chemical fluxes facilitating reactions which dictate their biological function. We explore how the morphology and component patterning are coupled through the competition of mean and Gaussian bending energies in multicomponent elastic shells that form three component irregular polyhedra. We observe two softer components with lower bending rigidities allocate on the edges and vertices while the harder component occupies the faces. When subjected to a non-zero interfacial line tension, the two softer components further separate and pattern into subdomains that are mediated by the Gaussian curvature. We find that this degree of fractionation is maximized when there is a weaker line tension and when the ratio of bending rigidities between the two softer domains $\approx 2$. Our results reveal a patterning mechanism in multicomponent shells that can capture the observed morphologies of bacterial microcompartments and, moreover, can be realized in synthetic vesicles.

Hybrid ionic-electronic conductors have the potential to generate memory effects and neuronal behavior. The functionality of these mixed materials depends on ion motion through thin polarizable channels. Here, we explore different polarization models to show that the current and conductivity of electrolytes is higher when confined by conductors than by dielectrics. We find non-linear currents in both dielectrics and conductors, and we recover the known linear (Ohmic) result only in the two-dimensional limit between conductors. We show that the polarization charge location impacts electrolyte structure and transport properties. This work suggests a mechanism to induce memristor hysteresis loops using conductor-dielectric switchable materials., Comment: 7 pages, 5 figures, A. P. dos Santos and F. Jim\'enez-\'Angeles contributed equally to this work and both are equal first authors

A droplet of a classical liquid surrounded by a cold gas placed on a hot substrate is accompanied by unremitting internal circulations, while the droplet remains immobile. Two identical cells with opposite sense of circulation form in the interior due to the thermocapillary effect induced by the gas and substrate temperature difference. Under the same conditions, a droplet composed of an odd viscous liquid exerts a compressive stress on the cell rotating in one sense and tensile on the cell rotating in the opposite sense resulting in a tilted droplet configuration. A sufficiently strong thermal gradient leads the contact angles to overcome hysteresis effects and induces droplet migration., Comment: 18 pages, 7 figures

Charged colloidal particles propel themselves through asymmetric fluxes of chemically generated ions on their surface. We show that asymmetry in the surface charge distribution introduces a new mode of self-phoretic motion 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 the particle surface. Janus nanoparticles endowed with both surface charge and ionic flux asymmetries results in enhanced propulsion speeds of the order of $\mu$m/s or higher. Our work provides a theoretical framework to quantitatively determine the velocity of asymmetrically charged nanoparticles undergoing ionic self-diffusiophoresis, and suggests an avenue for specifying surface properties that optimize and regulate self-propulsion in ionic media.

Stokesian Dynamics is a well-established computational method for simulating dynamics of many particles suspended in a conventional passive fluid medium. Active fluids composed of self-propelling particles with broken time reversal symmetry permit the emergence of a so-called odd viscosity. In this work, we extended the conventional Stokesian Dynamics formalism to incorporate the additional hydrodynamic effects due to odd viscosity, which enables simulating collective behaviors of many particles suspended in an active fluid medium with both even viscosity and odd viscosity.

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 fluid-like 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 wavepackets in vibrational motions of the large particles.

The development of multifunctional and biocompatible microrobots for biomedical applications relies on achieving locomotion through viscous fluids. Here, we describe a framework for swimming in homogeneous magnetoelastic membranes composed of superparamagnetic particles. By solving the equations of motion, we find the dynamical modes of circular membranes in precessing magnetic fields, which are found to actuate in or out of synchronization with a magnetic field precessing above or below a critical precession frequency, $\omega_c$, respectively. For frequencies larger than $\omega_c$, synchronized rotational and radial waves propagate on the membrane. These waves give rise to locomotion in an incompressible fluid at low Reynolds number using the lattice Boltzmann approach. Non-reciprocal motion resulting in swimming is achieved by breaking the morphological symmetry of the membrane, attained via truncation of a circular segment. The membrane translation can be adapted to a predetermined path by programming the external magnetic field. Our results lay the foundation for achieving directed motion in thin, homogeneous magnetoelastic membranes with a diverse array of geometries., Comment: 11 pages, 6 figures

Colloidal crystals formed by size-asymmetric binary particles co-assemble into a wide variety of colloidal compounds with lattices akin to ionic crystals. Recently, a transition from a compound phase with a sublattice of small particles to a metal-like phase in which the small particles are delocalized has been predicted computationally and observed experimentally. In this colloidal metallic phase, the small particles roam the crystal maintaining the integrity of the lattice of large particles, as electrons do in metals. A similar transition also occurs in superionic crystals, termed sublattice melting. Here, we use energetic principles and a generalized molecular dynamics model of a binary system of functionalized nanoparticles to analyze the transition to sublattice delocalization in different co-assembled crystal phases as a function of T, number of grafted chains on the small particles, and number ratio between the small and large particles $n_s$:$n_l$. We find that $n_s$:$n_l$ is the primary determinant of crystal type due to energetic interactions and interstitial site filling, while the number of grafted chains per small particle determines the stability of these crystals. We observe first-order sublattice delocalization transitions as T increases, in which the host lattice transforms from low- to high-symmetry crystal structures, including A20 to BCT to BCC, Ad to BCT to BCC, and BCC to BCC/FCC to FCC transitions and lattices. Analogous sublattice transitions driven primarily by lattice vibrations have been seen in some atomic materials exhibiting an insulator-metal transition also referred to as metallization. We also find minima in the lattice vibrations and diffusion coefficient of small particles as a function of $n_s$:$n_l$, indicating enhanced stability of certain crystal structures for $n_s$:$n_l$ values that form compounds., Comment: AE and HL-R contributed equally to this work

Spontaneous emergence of correlated states such as flocks and vortices are prime examples of remarkable collective dynamics and self-organization observed in active matter. The formation of globally correlated polar states in geometrically confined systems proceeds through the emergence of a macroscopic steadily rotating vortex that spontaneously selects a clockwise or counterclockwise global chiral state. Here, we reveal that a global vortex formed by colloidal rollers exhibits state memory. The information remains stored even when the energy injection is ceased and the activity is terminated. We show that a subsequent formation of the collective states upon re-energizing the system is not random. We combine experiments and simulations to elucidate how a combination of hydrodynamic and electrostatic interactions leads to hidden asymmetries in the local particle positional order encoding the chiral state of the system. The stored information can be accessed and exploited to systematically command subsequent polar states of active liquid through temporal control of the activity. With the chirality of the emergent collective states controlled on-demand, active liquids offer new possibilities for flow manipulation, transport, and mixing at the microscale., Comment: 19 pages, 10 figures

Near 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 interaction 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. This article provides analytical results, valid to first order in perturbation theory, for the self-energy of particles near a deformed near-flat interface. Explicit formulas are provided for the case of a sinusoidal deformation; generic deformations can then be treated by superposition. In addition to results for the self-energy, the surface polarization charge due to a single ion 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 curvature of the surface. Solid walls with a lower dielectric constant than the liquid repel all ions. We show here, however, that the repulsion is reduced by local convexity and enhanced by concavity; dimples are more repulsive than pimples.

Dielectric particles in weakly conducting fluids rotate spontaneously when subject to strong electric fields. Such Quincke rotation near a plane electrode leads to particle translation that enables physical models of active matter. Here, we show that Quincke rollers can also exhibit oscillatory dynamics, whereby particles move back and forth about a fixed location. We explain how oscillations arise for micron-scale particles commensurate with the thickness of a field-induced boundary layer in the nonpolar electrolyte. This work enables the design of colloidal oscillators.

Sublattice melting is the loss of order of one lattice component in binary or ternary ionic crystals upon increase in temperature. A related transition has been predicted in colloidal crystals. To understand the nature of this transition, we study delocalization in self-assembled, size asymmetric binary colloidal crystals using a generalized molecular dynamics model. Focusing on BCC lattices, we observe a smooth change from localized-to-delocalized interstitial particles for a variety of interaction strengths. Thermodynamic arguments, mainly the absence of a discontinuity in the heat capacity, suggest that the passage from localization-to-delocalization is continuous and not a phase transition. This change is enhanced by lattice vibrations, and the temperature of the onset of delocalization can be tuned by the strength of the interaction between the colloid species. Therefore, the localized and delocalized regimes of the sublattice are dominated by enthalpic and entropic driving forces, respectively. This work sets the stage for future studies of sublattice melting in colloidal systems with different stoichiometries and lattice types, and it provides insights into superionic materials, which have potential for application in energy storage technologies., Comment: Hector Lopez-Rios and Ali Ehlen contributed equally

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 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 the 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 surface polarization effect due to dielectric mismatch between the media inside and outside the confinement.

Water mediates electrostatic interactions via the orientation of its dipoles around ions, molecules, and interfaces. This induced water polarization consequently influences multiple phenomena. In particular, water polarization modulated by nanoconfinement affects ion adsorption and transport, biomolecular self-assembly, and surface chemical reactions. Therefore, it is of paramount importance to understand how water-mediated interactions change at the nanoscale. Here we show that near the graphene surface anion-cation interactions do not obey the translational and isotropic symmetries of Coulomb's law. We identify a new property, referred to as non-reciprocity, which describes the non-equivalent and directional interaction between two oppositely charged ions near the confining surface when their positions with respect to the interface are exchanged. Specifically, upon exchange of the two ions' positions along the surface normal direction the interaction energy changes by about 5$k_BT$. In both cases, confinement enhances the attraction between two oppositely charged ions near the graphene surface, while intercalation of one ion into the graphene layers shifts the interaction to repulsive. While the water permittivity in confinement is different from that in bulk, the effects observed here via molecular dynamics simulations and X-ray reflectivity experiments cannot be accounted for by current permittivity models. Our work shows that the water structure is not enough to infer electrostatic interactions near interfaces., Comment: 18 pages, 13 figures, Accepted in Physical Review Research

In superionic compounds one component pre-melts providing high ionic conductivity to solid state electrolytes. Here, we find sublattice melting in colloidal crystals of oppositely charged particles that are highly asymmetric in size and charge in salt solutions. The small particles in ionic compounds melt when the temperature increases forming a superionic phase. These delocalized small particles in a crystal of large oppositely charged particles, in contrast to superionic phases in atomic systems, form crystals with non-electroneutral stoichiometric ratios. This generates structures with multiple domains of ionic crystals in percolated superionic phases with adjustable stoichiometries.

Solid polymer electrolytes are considered a promising alternative to traditional liquid electrolytes in energy storage applications because of their good mechanical properties, and excellent thermal and chemical stability. A gap, however, still exists in understanding ion transport mechanisms and improving ion transport in solid polymer electrolytes. Therefore, it is crucial to bridge composition--structure and structure--property relationships. Here we demonstrate that size asymmetry, $\lambda$, represented by the ratio of counterion to charged monomer size, plays a key role in both the nanostructure and in the ionic dynamics. More specifically, when the nanostructure is modified by the external electric field such that the mobility cannot be described by linear response theory, two situations arise. The ionic mobility increases as $\lambda$ decreases (small counterions) in the weak electrostatics (high dielectric constant) regime. Whereas in systems with strong electrostatic interactions, ionomers with higher size symmetry ($\lambda \approx 1$) display higher ionic mobility. Moreover, ion transport is found to be dominated by the hopping of the ions and not by moving ionic clusters (also known as "vehicular'' charge transport). These results serve as a guide for designing ion-containing polymers for ion transport related applications.

We demonstrate that a highly charged polyelectrolyte confined in a spherical cavity undergoes reversible transformations between amorphous conformations to a four-fold symmetry morphology as a function of dielectric mismatch between the media inside and outside the cavity. Surface polarization due to dielectric mismatch exhibits an extra "confinement" effect, which are most pronounced within a certain range of the cavity radius and the electrostatic strength between the monomers and counterions and multivalent counterions. For cavities with a charged surface, surface polarization leads to an increased amount of counterions adsorbed in the outer side, further compressing the confined polyelectrolyte into a four-fold symmetry morphology. The equilibrium conformation of the chain is dependent upon several key factors including the relative permittivities of the media inside and outside the cavity, multivalent counterion concentration, cavity radius relative to the chain length, and interface charge density. Our findings offer insights into the effects of dielectric mismatch in packaging and delivery of polyelectrolytes across media with different relative permittivities. Moreover, the reversible transformation of the polyelectrolyte conformations in response to environmental permittivity allows for potential applications in biosensing and medical monitoring.

Polyelectrolytes under confinement are crucial for energy storage and for understanding biomolecular functions. Using molecular dynamics simulations, we analyze a polyelectrolyte solution confined between two oppositely charged planar dielectric surfaces and include surface polarization effects due to dielectric mismatch at the two electrodes. Although the effect of polarization on the charge distribution seems minor, we find that surface polarization enhances energy storage and also leads to the emergence of negative differential capacitance in confined polyelectrolyte solutions.

Elastic crystalline membranes exhibit a buckling transition from sphere to polyhedron. However, their morphologies are restricted to convex polyhedra and are difficult to externally control. Here, we study morphological changes of closed crystalline membrane of super-paramagnetic particles. The competition of magnetic dipole-dipole interactions with the elasticity of this magnetoelastic membrane leads to concave morphologies. Interestingly, as the magnetic field strength increases, the symmetry of the buckled membrane decreases from 5-fold to 3-fold, to 2-fold and, finally, to 1-fold rotational symmetry. This gives the ability to switch the membrane morphology between convex and concave shapes with specific symmetry and provides promising applications for membrane shape control in the design of actuatable micro-containers for targeted delivery systems.

We present a novel Ensemble Monte Carlo Growth method to sample the equilibrium thermodynamic properties of random chains. The method is based on the multicanonical technique of computing the density of states in the energy space. Such a quantity is temperature independent, and therefore microcanonical and canonical thermodynamic quantities, including the free energy, entropy, and thermal averages, can be obtained by re-weighting with a Boltzmann factor. The algorithm we present combines two approaches: the first is the Monte Carlo ensemble growth method, where a "population" of samples in the state space is considered, as opposed to traditional sampling by long random walks, or iterative single-chain growth. The second is the flat-histogram Monte Carlo, similar to the popular Wang-Landau sampling, or to multicanonical chain-growth sampling. We discuss the performance and relative simplicity of the proposed algorithm, and we apply it to known test cases., Comment: 7 pages, 6 figures; Added references and figures, corrected typos, improved notation

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, 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., Comment: J. Chem. Phys. (accepted)

Rebinding kinetics of molecular ligands plays a critical role in biomachinery, from regulatory networks to protein transcription, and is also a key factor for designing drugs and high-precision biosensors.In this study, we investigate initial release and rebinding of ligands to their binding sites grafted on a planar surface, a situation commonly observed in single molecule experiments and which occurs during exocytosis in vivo. Via scaling arguments and molecular dynamic simulations, we analyze the dependence of non-equilibrium rebinding kinetics on two intrinsic length scales: average separation distance between the binding sites and dimensions of diffusion volume (e.g., height of the experimental reservoir in which diffusion takes place or average distance between receptor-bearing surfaces). We obtain time-dependent scaling laws for on rates and for the cumulative number of rebinding events for various regimes. Our analyses reveal that, for diffusion-limited cases, the on rate decreases via multiple power law regimes prior to the terminal steady-state regime, in which the on rate becomes constant. At intermediate times, at which particle density has not yet become uniform throughout the reservoir, the number of rebindings exhibits a distinct plateau regime due to the three dimensional escape process of ligands from their binding sites. The duration of this regime depends on the average separation distance between binding sites. Following the three-dimensional diffusive escape process, a one-dimensional diffusive regime describes on rates. In the reaction-limited scenario, ligands with higher affinity to their binding sites delay the power laws. Our results can be useful for extracting hidden time scales in experiments where kinetic rates for ligand-receptor interactions are measured in microchannels, as well as for cell signaling via diffusing molecules., Comment: 14 pages, 9 figures, 1 table. Preprint

Elastic membranes composed of paramagnetic beads offer the possibility of assembling versatile actuators operated autonomously by external magnetic fields. Here we develop a theoretical framework to study shapes of such paramagnetic membranes under the influence of a fast precessing magnetic field. Their conformations are determined by the competition of the elastic and magnetic energies, arising as a result of their bending and the induced dipolar interactions between nearest neighbors beads. In the harmonic approximation, the elastic energy is quadratic in the surface curvatures. To account for the magnetic energy we introduce a continuum limit energy, quadratic in the projections of the surface tangents onto the precession axis. We derive the Euler-Lagrange equation governing the equilibria of these membranes, as well as the corresponding stresses. We apply this framework to examine paramagnetic membranes with quasiplanar, cylindrical, and helicoidal geometries. In all cases we found that their shape, energy, and stresses can be modified by means of the parameters of the magnetic field, mainly by the angle of precession., Comment: 9 pages, 6 figures

We examine analytically equilibrium conformations of elastic chains of paramagnetic beads in the presence of a precessing magnetic field. Conformations of these filaments are determined by minimizing their total energy, given in the harmonic approximation by the sum of the bending energy, quadratic in its curvature, and the magnetic dipolar interaction energy, quadratic in the projection of the vector tangent to the filament onto the precession axis. In particular, we analyze two families of open filaments with their ends aligned along the precession axis and described by segments of planar curves and helices. These configurations are characterized in terms of two parameters encoding their features such as their length, separation between their ends, as well as their bending and magnetic moduli, the latter being proportional to the magnitude and precession angle of the magnetic field. Based on energetic arguments, we present the set of parameter values for which each of these families of curves is probable to occur., Comment: 27 pages, 18 figures

Flexible superparamagnetic filaments are studied under the influence of fast precessing magnetic fields using simulations and a continuum approximation analysis. We find that individual filaments can be made to exert controllable tensile forces along the precession axis. These forces are exploited for microscopic actuation. In bulk, the filaments can be rapidly assembled into different configurations whose material properties depend on the field parameters. The precession frequency affects filament aggregation and conformation by changing the net torques on the filament ends. Using a time-dependent precession angle allows considerable freedom in choosing properties for filament aggregates. As an example, we design a field that twists chains together to dynamically assemble a self-healing gel., Comment: 8 pages, 3 figures

We study unbinding of multivalent cationic ligands from oppositely charged polymeric binding sites sparsely grafted on a flat neutral substrate. Our molecular dynamics (MD) simulations are suggested by single-molecule studies of protein-DNA interactions. We consider univalent salt concentrations spanning roughly a thousandfold range, together with various concentrations of excess ligands in solution. To reveal the ionic effects on unbinding kinetics of spontaneous and facilitated dissociation mechanisms, we treat electrostatic interactions both at a Debye-H\"{u}ckel (DH, or `implicit' ions, i.e., use of an electrostatic potential with a prescribed decay length) level, as well as by the more precise approach of considering all ionic species explicitly in the simulations. We find that the DH approach systematically overestimates unbinding rates, relative to the calculations where all ion pairs are present explicitly in solution, although many aspects of the two types of calculation are qualitatively similar. For facilitated dissociation (FD, acceleration of unbinding by free ligands in solution) explicit ion simulations lead to unbinding at lower free ligand concentrations. Our simulations predict a variety of FD regimes as a function of free ligand and ion concentrations; a particularly interesting regime is at intermediate concentrations of ligands where non-electrostatic binding strength controls FD. We conclude that explicit-ion electrostatic modeling is an essential component to quantitatively tackle problems in molecular ligand dissociation, including nucleic-acid-binding proteins., Comment: 14 pages, 6 figures, regular article. An additional grant information has been added on 11/3/2017

We provide exact expressions for the electrostatic energy of uniformly-charged prolate and oblate spheroidal shells. We find that uniformly-charged prolate spheroids of eccentricity greater than 0.9 have lower Coulomb energy than a sphere of the same area. For the volume-constrained case, we find that a sphere has the highest Coulomb energy among all spheroidal shells. Further, we derive the change in the Coulomb energy of a uniformly-charged shell due to small, area-conserving perturbations on the spherical shape. Our perturbation calculations show that buckling-type deformations on a sphere can lower the Coulomb energy. Finally, we consider the possibility of counterion condensation on the spheroidal shell surface. We employ a Manning-Oosawa two-state model approximation to evaluate the renormalized charge and analyze the behavior of the equilibrium free energy as a function of the shell's aspect ratio for both area-constrained and volume-constrained cases. Counterion condensation is seen to favor the formation of spheroidal structures over a sphere of equal area for high values of shell volume fractions., Comment: 15 pages, 7 figures, Accepted in Physical Review E

In the study of model electronic device systems where electrons are typically under confinement, a key obstacle is the need to iteratively solve the coupled Schr\"{o}dinger-Poisson (SP) equation. It is possible to bypass this obstacle by adopting a variational approach and obtaining the solution of the SP equation by minimizing a functional. Further, using molecular dynamics methods that treat the electronic potential as a dynamical variable, the functional can be minimized on the fly in conjunction with the update of other dynamical degrees of freedom leading to considerable reduction in computational costs. But such approaches require access to a true free-energy functional, one that evaluates to the equilibrium free energy at its minimum. In this paper, we present a variational formulation of the Schr\"{o}dinger-Poisson (SP) theory with the needed free-energy functional of the electronic potential. We apply our formulation to semiconducting nanostructures and provide the expression of the free-energy functional for narrow channel quantum wells where the local density approximation yields accurate physics and for the case of wider channels where Thomas-Fermi approximation is valid., Comment: 7 pages, 2 figures

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., Comment: 3 figures

Manipulating the shape of nanoscale objects in a controllable fashion is at the heart of designing materials that act as building blocks for self-assembly or serve as targeted drug delivery carriers. Inducing shape deformations by controlling external parameters is also an important way of designing biomimetic membranes. In this paper, we demonstrate that electrostatics can be used as a tool to manipulate the shape of soft, closed membranes by tuning environmental conditions such as the electrolyte concentration in the medium. Using a molecular dynamics-based simulated annealing procedure, we investigate charged elastic shells that do not exchange material with their environment, such as elastic membranes formed in emulsions or synthetic nanocontainers. We find that by decreasing the salt concentration or increasing the total charge on the shell's surface, the spherical symmetry is broken, leading to the formation of ellipsoids, discs, and bowls. Shape changes are accompanied by a significant lowering of the electrostatic energy and a rise in the surface area of the shell. To substantiate our simulation findings, we show analytically that a uniformly charged disc has a lower Coulomb energy than a sphere of the same volume. Further, we test the robustness of our results by including the effects of charge renormalization in the analysis of the shape transitions and find the latter to be feasible for a wide range of shell volume fractions., Comment: 6 pages, 4 figures