We consider an osmotic equilibrium between bulk solutions of polyelectrolyte bounded by semipermeable membranes and separated by a thin film of salt-free liquid. Although the membranes are neutral, the counter-ions of the polyelectrolyte molecules permeate into the gap and lead to a steric charge separation. This gives rise to a distance-dependent membrane potential, which translates into a repulsive electrostatic disjoining pressure. From the solution of the non-linear Poisson-Boltzmann equation we obtain the distribution of the potential and of ions. We then derive an explicit formula for the pressure exerted on the membranes and show that it deviates from the classical van't Hoff expression for the osmotic pressure. This difference is interpreted in terms of a repulsive electrostatic disjoining pressure originating from the overlap of counterion clouds inside the gap. We also develop a simplified theory based on a linearized Poisson-Boltzmann approach. A comparison with simulation of a primitive model for the electrolyte is provided and does confirm the validity of the theoretical predictions Beyond the fundamental result that the neutral surfaces can repel, this mechanism not only helps to control the adhesion and long-range interactions of living cells, bacteria, and vesicles, but also allows us to argue that electrostatic interactions should play enormous role in determining behavior and functions of systems bounded by semipermeable membranes.
We study a model for macroions in an electrolyte solution confined by a semipermeable membrane. The membrane finite thickness is considered and both membrane surfaces are uniformly charged. The model explicitly includes electrostatic and size particles correlations. Our study is focused on the adsorption of macroions on the membrane surface and on the osmotic pressure. The theoretical prediction for the osmotic pressure shows a good agreement with experimental results.
We consider an electrolyte solution confined by semipermeable membranes in contact with a salt-free solvent. Membranes are uncharged, but since small counter-ions leak-out into infinite salt-free reservoirs, we observe a distance-dependent membrane potential, which generates a repulsive electrostatic disjoining pressure. We obtain the distribution of the potential and of ions, and derive explicit formulas for the disjoining pressure, which are validated by computer simulations. We predict a strong short-range power-law repulsion, and a weaker long-range exponential decay. Our results also demo…
We consider two charged semipermeable membranes, which bound bulk electrolyte solutions and are separated by a thin film of salt-free liquid. Small counter-ions permeate into the gap, which leads to a steric charge separation in the system. To quantify the problem, we define an effective surface charge density of imaginary impermeable surface, which mimics an actual semipermeable membrane and greatly simplify analysis. The effective charge depends on separation, generally differ from the real one, and could even be of the opposite sign. From the exact and asymptotic solutions of the nonlinear …
We investigate effective interactions between a colloidal particle, immersed in a binary mixture of smaller spheres, and a semipermeable membrane. The colloid is modeled as a big hard sphere and the membrane is represented as an infinitely thin surface which is fully permeable to one of the smaller spheres and impermeable to the other one. Within the framework of the density functional theory we evaluate the depletion potentials, and we consider two different approximate theories - the simple Asakura-Oosawa approximation and the accurate White-Bear version of the fundamental measure theory. Th…
In this paper we study the electrostatic interaction of a heterogeneously charged wall with a neutral semipermeable membrane. The wall consists of periodic stripes, where the charge density varies in one direction. The membrane is in a contact with a bulk reservoir of an electrolyte solution and separated from the wall by a thin film of salt-free liquid. One type of ions (small counterions) permeates into the gap and gives rise to a distance-dependent membrane potential, which translates into a repulsive electrostatic disjoining pressure due to an overlap of counterion clouds in the gap. To qu…
Lipid bilayer membranes have a native (albeit small) permeability for water molecules. Under an external load, provided that the bilayer structure stays intact and does not suffer from poration or rupture, a lipid membrane deforms and its water influx/efflux is often assumed negligible in the absence of osmolarity. In this work we use boundary integral simulations to investigate the effects of water permeability on the vesicle hydrodynamics due to a mechanical load, such as the viscous stress from an external flow deforming a vesicle membrane in free space or pushing it through a confinement. …
We probe the electrostatic cost associated with the approach phase of DNA translocation events. Within an analytical theory at the Debye-Huckel level, we calculate the electrostatic free energy of a rigid DNA molecule interacting with a dielectric membrane. For carbon or silicon based low permittivity neutral membranes, the DNA molecule experiences a repulsive energy barrier between 10 kBT and 100 kBT. In the case of engineered membranes with high dielectric permittivity, the membrane surface attracts the DNA with an energy of the same magnitude. Both the repulsive and attractive interactions …
We investigate the effect on biomembrane mechanical properties due to the presence an external potential for a non-conductive non-compressible membrane surrounded by different electrolytes. By solving the Debye-Huckel and Laplace equations for the electrostatic potential and using the relevant stress-tensor we find: in (1.) the small screening length limit, where the Debye screening length is smaller than the distance between the electrodes, the screening certifies that all electrostatic interactions are short-range and the major effect of the applied potential is to decrease the membrane tens…
We study the non-equilibrium dynamics of lipid membranes with proteins that actively pump ions across the membrane. We find that the activity leads to a fluctuating force distribution due to electrostatic interactions arising from variation in dielectric constant across the membrane. By applying a multipole expansion we find effects on both the tension and bending rigidity dominated parts of the membranes fluctuation spectrum. We discuss how our model compares with previous studies of force-multipole models.
We consider the influence of electrostatic forces on driven translocation dynamics of a flexible polyelectrolyte being pulled through a nanopore by an external force on the head monomer. To this end, we augment the iso-flux tension propagation (IFTP) theory with electrostatics for a negatively charged biopolymer pulled through a nanopore embedded in a similarly charged anionic membrane. We show that for the realistic case such as a single-stranded DNA, the translocation dynamics at low salt where screening is weak and at finite negative membrane charge is unexpectedly accelerated despite the l…
Bending rigidity of a charged membrane or a charged polyelectrolyte screened by monovalent counterions is known to be enhanced by electrostatic effects. We show that in the case of screening by multivalent counterions the electrostatic effects reduce the bending rigidity. This inversion of the sign of the electrostatic contribution is related to the formation of two-dimensional strongly correlated liquids (SCL) of counterions at the charged surface due to strong lateral repulsion between them. When a membrane or a polyelectrolyte is bent, SCL is compressed on one side and stretched on the othe…
We characterize the role of charge correlations in the adsorption of a short, rod-like anionic polyelectrolyte onto a similarly charged membrane. Our theory reveals two different mechanisms driving the like-charge polyelectrolyte-membrane complexation: in weakly charged membranes, repulsive polyelectrolyte-membrane interactions lead to the interfacial depletion and a parallel orientation of the polyelectrolyte with respect to the membrane; while in the intermediate membrane charge regime, the interfacial counterion excess gives rise to an attractive "salt-induced" image force. This furthermore…
We characterize the role of electrostatic fluctuations on the charge selectivity of cylindrical nanopores confining electrolyte mixtures. To this end, we develop an extended one-loop theory that can account for correlation effects induced by the surface charge, nanoconfinement of the electrolyte, and interfacial polarization charges associated with the low permittivity membrane. We validate the quantitative accuracy of the theory by comparisons with previously obtained Monte-Carlo simulation data from the literature, and scrutinize in detail the underlying forces driving the ionic selectivity …
We consider the electrostatic interaction between two rigid membranes, with different surface charge densities of opposite sign, across an aqueous solution without added salt. Exact solutions to the nonlinear Poisson-Boltzmann equation are obtained and their physical meaning discussed. We also calculate the electrostatic contribution to the free energy and discuss the renormalization of the area per head group of the charged lipids arising from the Coulomb interaction.
We discuss the electrostatic contribution to the elastic moduli of a cell or artificial membrane placed in an electrolyte and driven by a DC electric field. The field drives ion currents across the membrane, through specific channels, pumps or natural pores. In steady state, charges accumulate in the Debye layers close to the membrane, modifying the membrane elastic moduli. We first study a model of a membrane of zero thickness, later generalizing this treatment to allow for a finite thickness and finite dielectric constant. Our results clarify and extend the results presented in [D. Lacoste, …
We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attra…
The electrostatic Schwinger-Dyson equations are derived and solved for an electrolyte mixture composed of mono- and multivalent ions confined to a negatively charged nanoslit. The closure of these equations is based on an asymmetric treatment of the ionic species with respect to their electrostatic coupling strength; the weakly coupled monovalent ions are treated within a gaussian approximation while the multivalent counterions of high coupling strength are incorporated with a strong-coupling approach. The resulting self-consistent formalism includes explicitly the interactions of the multival…
We present theoretical work in which the degree of electrostatic coupling across a charged lipid bilayer in aqueous solution is analyzed on the basis of nonlinear Poisson-Boltzmann theory. In particular, we consider the electrostatic interaction of a single, large macroion with the two apposed leaflets of an oppositely charged lipid bilayer where the macroion is allowed to optimize its distance to the membrane. Three regimes are identified: a weak and a high macroion charge regime, separated by a regime of close macroion-membrane contact for intermediate charge densities. The corresponding fre…
We extend Van't Hoff's law for the osmotic pressure to a suspension of active Brownian particles. The propelled particles exert a net reaction force on the solvent, and thereby either drive a measurable solvent flow from the connecting solvent reservoir through the semipermeable membrane, or increase the osmotic pressure and cause the suspension to rise to heights as large as micrometers for experimentally realized microswimmers described in the literature. The increase in osmotic pressure is caused by the background solvent being, in contrast to passive suspensions, no longer at the chemical …
We use a coarse-grained molecular dynamics simulation to investigate the interaction between neutral or charged nanoparticles (NPs) and a vesicle consisting of neutral and negatively charged lipids. We focus on the interaction strengths of hydrophilic and hydrophobic attraction and electrostatic interactions between a lipid molecule and an NP. A neutral NP passes through the lipid membrane when the hydrophobic interaction is sufficiently strong. As the valence of the positively charged NP increases, the membrane permeation speed of the NP is increased compared with the neutral NP and charged l…
In ion-exchange membrane processes, ions and water flow under the influence of gradients in hydrostatic pressure, ion chemical potential, and electrical potential (voltage), leading to solvent flow, ionic fluxes and ionic current. At the outer surfaces of the membranes, electrical double layers (EDLs) are formed (Donnan layers). When a current flows through the membrane, we argue that besides Joule heating in the bulk of the membrane and in the electrolyte outside the membrane, there is also electrostatic heating and cooling in the EDLs. In addition, when fluid flows through a charged membrane…
We probe the electrostatic mechanism driving adsorption of polyelectrolytes onto like-charged membranes upon the addition of tri- and tetravalent counterions to a bathing monovalent salt solution. We develop a one-loop-dressed strong coupling theory that treats the monovalent salt at the electrostatic one-loop level and the multivalent counterions within a strong-coupling approach. It is shown that the adhesive force of the multivalent counterions mediating the like-charge adsorption arises from their strong condensation at the charged membrane. The resulting interfacial counterion excess loca…
We investigate the electrostatic interactions of zwitterionic membranes immersed in mixed electrolytes composed of mono- and multivalent ions. We show that the presence of monovalent salt is a necessary condition for the existence of a finite electrostatic force on the membrane. As a result, the mean-field membrane pressure originating from the surface dipoles exhibits a non-uniform salt dependence, characterized by an enhancement for dilute salt conditions and a decrease at intermediate salt concentrations. Upon addition of multivalent cations to the submolar salt solution, the separate inter…
A model of a finite cylindrical ion channel through a phospholipid membrane of width $L$ separating two electrolyte reservoirs is studied. Analytical solution of the Poisson equation is obtained for an arbitrary distribution of ions inside the trans-membrane pore. The solution is asymptotically exact in the limit of large ionic strength of electrolyte on the two sides of membrane. However, even for physiological concentrations of electrolyte, the electrostatic barrier sizes found using the theory are in excellent agreement with the numerical solution of the Poisson equation. The analytical sol…
Sensitive sequencing of biopolymers by nanopore-based translocation techniques requires extension of the time spent by the molecule in the pore. We develop an electrostatic theory of polymer translocation to show that the translocation time can be extended via the dielectric trapping of the polymer. In dilute salt conditions, the dielectric contrast between the low permittivity membrane and large permittivity solvent gives rise to attractive interactions between the cis and trans portions of the polymer. This self-attraction acts as a dielectric trap that can enhance the translocation time by …
Within a dipolar Poisson-Boltzmann theory including electrostatic correlations, we consider the effect of explicit solvent structure on solvent and ion partition confined to charged nanopores. We develop a relaxation scheme for the solution of this highly non-linear integro-differential equation for the electrostatic potential. The scheme is an extension of the approach previously introduced for simple planes (S. Buyukdagli and Ralf Blossey, J. Chem. Phys. 140, 234903 (2014)) to nanoslit geometry. We show that the reduced dielectric response of solvent molecules at the membrane walls gives ris…
We propose a very simple but realistic enough model which allows to include a large number of molecules in molecular dynamics MD simulations of these bilayers, but nevertheless taking into account molecular charge distributions, flexible amphiphilic molecules and a reliable model of water. All these parameters are essential in a nanoscopic scale study of intermolecular and long range electrostatic interactions. This model was previously used by us to simulate a Newton black film and in this paper we extend our investigation to bilayers of the biological membrane type. The electrostatic interac…
The electrostatic screening of charge in one-dimensional confinement leads to long-range breakdown in electroneutrality within a nanopore. Through a series of continuum simulations, we demonstrate the principles of electroneutrality breakdown for electrolytes in one dimensional confinement. We show how interacting pores in a membrane can counteract the phenomenon of electroneutrality breakdown, eventually returning to electroneutrality. Emphasis is placed on applying simplifying formulas to reduce the multidimensional partial differential equations into a single ordinary differential equation …
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 …
This paper considers the effect of electrostatics on the stability of a charged membrane. We show that at low ionic strength and high surface charge density, repulsion between charges on the membrane renders it unstable to the formation of holes. A free straight edge is unstable to modulations with wavelength longer than the Debye screening length. Hence at low ionic strength, membranes will disintegrate into vesicles. We use these results to interpret stable holes in red blood cell ghosts (Steck et. al., Science 168:255(1970)).
Translocation properties of ionic channels are investigated, on the basis of classical electrostatics, with an emphasis on asymptotic formulas for the potential and field associated with a point charge in the channel. Due to image charges in the membrane, we show that ions in an infinite length channel interact via a one-dimensional (1D) Coulomb potential. The corresponding electrostatic barrier $Σ$ is characterized by a "geometric mean" screening $Σ\propto e^2 / \sqrt{ε_w ε_m}R$ ($R$ being the radius of the pore, and $ε_m \approx 2$ and $ε_w \approx 80$ the room temperature dielectric constan…
Motivated by biological membrane-containing organelles in plants and photosynthetic bacteria, we study charge regulation in a model membrane stack. Considering (de)protonation as the simplest mechanism of charge equilibration between the membranes and with the bathing environment, we uncover a symmetry-broken charge state in the stack with a quasiperiodic effective charge sequence. In the case of a monovalent bathing salt solution our model predicts complex, inhomogeneous charge equilibria depending on the strength of the (de)protonation reaction, salt concentration, intermembrane separation, …
Self-propulsion (SP) is a main feature of active particles (AP), such as bacteria or biological micromotors, distinguishing them from passive colloids. A renowned consequence of SP is accumulation at static interfaces, even in the absence of hydrodynamic interactions. Here we address the role of SP in the interaction between AP and a moving semipermeable membrane. In particular, we implement a model of noninteracting AP in a channel crossed by a partially penetrable wall, moving at a constant velocity $c$. With respect to both the cases of passive colloids with $c>0$ and AP with $c=0$, the AP …
We consider a mixture of one neutral and two oppositely charged types of molecules confined to a surface. Using analytical techniques and molecular dynamics simulations, we construct the phase diagram of the system and exhibit the coexistence between a patterned solid phase and a charge-dilute phase. The patterns in the solid phase arise from competition between short-range immiscibility and long-range electrostatic attractions between the charged species. The coexistence between phases leads to observations of stable patterned domains immersed in a neutral matrix background.
We study the strong-coupling (SC) interaction between two like-charged membranes of finite thickness embedded in a medium of higher dielectric constant. A generalized SC theory is applied along with extensive Monte-Carlo simulations to study the image charge effects induced by multiple dielectric discontinuities in this system. These effects lead to strong counterion crowding in the central region of the inter-surface space upon increasing the solvent/membrane dielectric mismatch and change the membrane interactions from attractive to repulsive at small separations. These features agree quanti…
We develop a model of interacting zwitterionic membranes with rotating surface dipoles immersed in a monovalent salt, and implement it in a field theoretic formalism. In the mean-field regime of monovalent salt, the electrostatic forces between the membranes are characterized by a non-uniform trend: at large membrane separations, the interfacial dipoles on the opposing sides behave as like-charge cations and give rise to repulsive membrane interactions; at short membrane separations, the anionic field induced by the dipolar phosphate groups sets the behavior in the intermembrane region. The at…
We consider a system composed of a monodisperse charge-stabilized colloidal suspension in the presence of monovalent salt, separated from the pure electrolyte by a semipermeable membrane, which allows the crossing of solvent, counterions, and salt particles, but prevents the passage of polyions. The colloidal suspension, that is in a crystalline phase, is considered using a spherical Wigner-Seitz cell. After the Donnan equilibrium is achieved, there will be a difference in pressure between the two sides of the membrane. Using the functional density theory, we obtained the expression for the os…
We predict the nature (attractive or repulsive) and range (exponentially screened or long-range power law) of the electrostatic interactions of oppositely charged and planar plates as a function of the salt concentration and surface charge densities (whose absolute magnitudes are not necessarily equal). An analytical expression for the crossover between attractive and repulsive pressure is obtained as a function of the salt concentration. This condition reduces to the high-salt limit of Parsegian and Gingell where the interaction is exponentially screened and to the zero salt limit of Lau and …
Lipid rafts are hypothesized to facilitate protein interaction, tension regulation, and trafficking in biological membranes, but the mechanisms responsible for their formation and maintenance are not clear. Insights into many other condensed matter phenomena have come from colloidal systems, whose micron-scale particles mimic basic properties of atoms and molecules but permit dynamic visualization with single-particle resolution. Recently, experiments showed that bidisperse mixtures of filamentous viruses can self-assemble into colloidal monolayers with thermodynamically stable rafts exhibitin…
Using integral equation theory of liquids to a binary mixed fluid lipid membrane, we study the membrane-mediated interactions between the macroions and the redistribution of neutral and charged lipids due to binding macroions. We find that when the concentration of binding macroions is infinitely dilute, the main contribution to the attractive potential between macroions is the line tension between neutral and charged lipids of the membrane, and the bridging effect also contributes to the attraction. As the relative concentration of charged lipids is increased, we observe a repulsive - attract…
Polymer translocation experiments typically involve anionic polyelectrolytes such as DNA molecules driven through negatively charged nanopores. Quantitative modelling of polymer capture to the nanopore followed by translocation therefore necessitates the consideration of the electrostatic barrier resulting from like-charge polymer-pore interactions. To this end, in this work we couple mean-field level electrohydrodynamic equations with the Smoluchowski formalism to characterize the interplay between the electrostatic barrier, the electrophoretic drift, and the electro-osmotic liquid flow. In p…
We formulate a theory of electrostatic interactions in lipid bilayer membranes where both monolayer leaflets contain dissociable moieties that are subject to charge regulation. We specifically investigate the coupling between membrane curvature and charge regulation of a lipid bilayer vesicle using both the linear Debye-Hückel (DH) and the non-linear Poisson-Boltzmann (PB) theory. We find that charge regulation of an otherwise symmetric bilayer membrane can induce charge symmetry breaking, non-linear flexoelectricity and anomalous curvature dependence of free energy. The pH effects investigate…
In this chapter we review the electrostatic properties of charged membranes in aqueous solutions, with or without added salt, employing simple physical models. The equilibrium ionic profiles close to the membrane are governed by the well-known Poisson-Boltzmann (PB) equation. We analyze the effect of different boundary conditions, imposed by the membrane, on the ionic profiles and the corresponding osmotic pressure. The discussion is separated into the single membrane case and that of two interacting membranes. For one membrane setup, we show the different solutions of the PB equation and disc…
Understanding the influence of hydrodynamic stresses and colloidal interactions between droplets and membranes will inform better engineered membrane surfaces and process conditions. Using a long-wave hydrodynamic description that incorporates wettability and electrostatic repulsion, we numerically investigate the influence of droplet shapes and membrane characteristics on the overall repulsion-attraction towards the membrane surface. A stability phase diagram classifies stable-unstable drop shapes and investigate whether there is reversible deposition of droplets onto the membrane.
There are three regimes of cell membrane interaction with glass - Tight and loose adhesion, separated by repulsion. Explicitly including hydration, this paper evaluates the pressure between the surfaces as functions of distance for ion-correlation and ion-screened electrostatics, and electromagnetic fluctuations. The results agree with data for tight adhesion energy (0.5-3 vs 0.4-4 mJ/m2), detachment pressure (7.9 vs 9 MPa), and peak repulsion (3.4-7.5 vs 5-10 kPa), also matching the repulsion's distance dependence upon renormalization by steric pressure mainly from undulations.
We study the contribution of polyelectrolytes in solution to the bending moduli of charged membranes. Using the Helfrich free energy, and within the mean-field theory, we calculate the dependence of the bending moduli on the electrostatics and short-range interactions between the membrane and the polyelectrolyte chains. The most significant effect is seen for strong short-range interactions and low amounts of added salt where a substantial increase in the bending moduli of order $1 k_BT$ is obtained. From short-range repulsive membranes, the polyelectrolyte contribution to the bending moduli i…
Understanding interactions between membranes requires measurements on well-controlled systems close to natural conditions, in which fluctuations play an important role. We have determined, by grazing incidence X-ray scattering, the interaction potential between two lipid bilayers, one adsorbed on a solid surface and the other floating close by. We find that interactions in this highly hydrated model system are two orders of magnitude softer than in previously reported work on multilayer stacks. This is attributed to the weak electrostatic repulsion due to the small fraction of ionized lipids i…
The computational study of the interaction between charged, ligand-protected metal nanoparticles and model lipid membranes has been recently addressed both at atomistic and coarse grained level. Here we compare the performance of three versions of the coarse grained Martini force field at describing the nanoparticle-membrane interaction. The three coarse-grained models differ in terms of treatment of long-range electrostatic interactions and water polarizability. The NP-membrane interaction consists in the transition from a metastable NP- membrane complex, in which the NP is only partially emb…
We have studied the electrostatic screening effect of NaCl solutions on the interactions between anionic lipid bilayers in the fluid lamellar phase using a Poisson-Boltzmann based mean-field approach with constant charge and constant potential limiting charge regulation boundary conditions. The full DLVO potential, including the electrostatic, hydration and van der Waals interactions, was coupled to thermal bending fluctuations of the membranes via a variational Gaussian Ansatz. This allowed us to analyze the coupling between the osmotic pressure and the fluctuation amplitudes and compare them…
Integral membrane proteins deform the surrounding bilayer creating long-ranged forces that influence distant proteins. These forces can be attractive or repulsive, depending on the proteins' shape, height, contact angle with the bilayer, as well as the local membrane curvature. Although interaction energies are not pairwise additive, for sufficiently low protein density, thermodynamic properties depend only upon pair interactions. Here, we compute pair interaction potentials and entropic contributions to the two-dimensional osmotic pressure of a collection of noncircular proteins. In contrast …
It has been known that the uptake mechanisms of cell-penetrating peptides(CPPs) depend on the experimental conditions such as concentration of peptides, lipid composition, temperature, etc. In this study we investigate the temperature dependence of the penetration of Arg9s into a DOPC/DOPG(4:1) membrane using molecular dynamics(MD) simulations at two different temperatures, T = 310 K and T = 288 K. Although it is difficult to identify the temperature dependence because of having only one single simulation at each temperature and no evidence of translocation of Arg9s across the membrane at both…
Using a lattice model and a versatile thermodynamic integration scheme, we study the critical Casimir interactions between inclusions embedded in a two-dimensional critical binary mixtures. For single-domain inclusions we demonstrate that the interactions are very long range, and their magnitudes strongly depend on the affinity of the inclusions with the species in the binary mixtures, ranging from repulsive when two inclusions have opposing affinities to attractive when they have the same affinities. When one of the inclusions has no preference for either of the species, we find negligible cr…
Ionic microgels are soft colloidal particles, composed of crosslinked polymer networks, that ionize and swell when dispersed in a good solvent. Swelling of these permeable, compressible particles involves a balance of electrostatic, elastic, and mixing contributions to the single-particle osmotic pressure. The electrostatic contribution depends on the distributions of mobile counterions and coions and of fixed charge on the polymers. Within the cell model, we employ two complementary methods to derive the electrostatic osmotic pressure of ionic microgels. In Poisson-Boltzmann (PB) theory, we m…
Cationic lipid membranes are known to form compact complexes with DNA and to be effective as gene delivery agents both in vitro and in vivo. Here we employ molecular dynamics simulations for a detailed atomistic study of lipid bilayers consisting of a mixture of cationic dimyristoyltrimethylammonium propane (DMTAP) and zwitterionic dimyristoylphosphatidylcholine (DMPC). Our main objective is to examine how the composition of the bilayers affects their structural and electrostatic properties in the liquid-crystalline phase. By varying the mole fraction of DMTAP, we have found that the area per …
The Derjaguin-Landau-Verywey-Overbeek (DLVO) theory has been a remarkably accurate framework for the characterization of macromolecular stability in water solvent. In view of its solvent-implicit nature neglecting the electrostatics of water molecules with non-negligible charge structure and concentration, the precision of the DLVO formalism is somewhat puzzling. In order to shed light on this issue, we derive from our earlier explicit solvent formalism [S. Buyukdagli el al., Phys. Rev. E, 2013, 87, 063201] a solvent-augmented contact value theorem and assess the contribution of solvent molecu…
