arXiv subjects

Arghya Majee

Publications and source records attributed to Arghya Majee.

At least 19 recordsLinked to original sources

arXiv2024

Charge separation at liquid interfaces

We present a theory for phase-separated liquid coacervates with salt, taking into account spatial heterogeneities and interfacial profiles. We find that charged layers of alternating sign can form around the interface while the bulk phases remain approximately charge-neutral. We show that the salt concentration regulates the number of layers and the amplitude of the layer's charge density and electrostatic potential. Such charged layers can either repel or attract single-charged molecules diffusing across the interface. Our theory could be relevant for artificial systems and biomolecular condensates in cells. Our work suggests that interfaces of biomolecular condensates could mediate charge-specific transport similar to membrane-bound compartments.

cond-mat.soft↗

arXiv2023

Electrostatic interactions between charge regulated spherical macroions

We study the interaction between two charge regulating spherical macroions with dielectric interior and dissociable surface groups immersed in a monovalent electrolyte solution. The charge dissociation is modelled via the Frumkin-Fowler-Guggenheim isotherm, which allows for multiple adsorption equilibrium states. The interactions are derived from the solutions of the mean-field Poisson-Boltzmann type theory with charge regulation boundary conditions. For a range of conditions we find symmetry breaking transitions from symmetric to asymmetric charge distribution exhibiting annealed charge patchiness, which results in like-charge attraction even in a univalent electrolyte -- thus fundamentally modifying the nature of electrostatic interactions in charge-stabilized colloidal suspensions.

cond-mat.soft↗

arXiv2023

Curvature effects in interfacial acidity of amphiphilic vesicles

We analyze the changes in the vicinal acidity (pH) at a spherical amphiphilic membrane. The membrane is assumed to contain solvent accessible, embedded, dissociable, charge regulated moieties. Basing our approach on the linear Debye-Hückel as well as the non-linear Poisson-Boltzmann theory, together with the general Frumkin-Fowler-Guggenheim adsorption isotherm model of the charge regulation process, we analyse and review the dependence of the local pH on the position, as well as bulk electrolyte concentration, bulk pH and curvature of the amphiphilic single membrane vesicle. With appropriately chosen adsorption parameters of the charge regulation model, we find a good agreement with available experimental data.

cond-mat.soft↗

arXiv2022

Electroviscous drag on squeezing motion in sphere-plane geometry

Theoretically and experimentally, we study electroviscous phenomena resulting from charge-flow coupling in a nanoscale capillary. Our theoretical approach relies on Poisson-Boltzmann mean-field theory and on coupled linear relations for charge and hydrodynamic flows, including electro-osmosis and charge advection. With respect to the unperturbed Poiseuille flow, we define an electroviscous coupling parameter $ξ$, which turns out to be maximum where the film thickness $h_0$ is comparable to the screening length $λ$. We also present dynamic AFM data for the visco-elastic response of a confined water film in sphere-plane geometry; our theory provides a quantitative description for the electroviscous drag coefficient and the electrostatic repulsion as a function of the film thickness, with the surface charge density as the only free parameter. Charge regulation sets in at even smaller distances.

physics.flu-dyn↗

arXiv2022

Curvature effects in charge-regulated lipid bilayers

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 investigated go beyond the paradigm of electrostatic renormalization of the mechano-elastic properties of membranes.

cond-mat.soft↗

arXiv2020

Charge symmetry broken complex coacervation

Liquid-liquid phase separation has emerged as one of the important paradigms in the chemical physics as well as biophysics of charged macromolecular systems. We elucidate an equilibrium phase separation mechanism based on charge regulation, i.e., protonation-deprotonation equilibria controlled by pH, in an idealized macroion system which can serve as a proxy for simple coacervation. First, a low-density density-functional calculation reveals the dominance of two-particle configurations coupled by ion adsorption on neighboring macroions. Then a binary cell model, solved on the Debye-Hückel as well as the full nonlinear Poisson-Boltzmann level, unveils the charge-symmetry breaking as inducing the phase separation between low- and high-density phases as a function of pH. These results can be identified as a charge symmetry broken complex coacervation between chemically identical macroions.

cond-mat.soft↗

arXiv2020

Electrostatic pair-interaction of nearby metal or metal-coated colloids at fluid interfaces

In this paper, we theoretically study the electrostatic interaction between a pair of identical colloids with constant surface potentials sitting in close vicinity of each other at a fluid interface. By employing a simplified yet reasonable model system, the problem is solved within the framework of classical density functional theory and linearized as well as nonlinear Poisson-Boltzmann (PB) theory. Apart from providing a sound theoretical framework generally applicable to any such problem, our novel findings, all of which contradict common beliefs, include the following: first, quantitative as well as qualitative differences between the interactions obtained within the linear and the nonlinear PB theories; second, the importance of the electrostatic interaction between the omnipresent three-phase contact lines in interfacial systems; and third, the occurrence of an attractive electrostatic interaction between a pair of identical metal colloids. The unusual attraction we report on largely stems from an attractive line interaction which although scales linearly with the size of the particle, can compete with the surface interactions and can be strong enough to alter the nature of the total electrostatic interaction. Our results should find applications in metal or metal-coated particle-stabilized emulsions where densely packed particle arrays are not only frequently observed but are sometimes required.

cond-mat.soft↗

arXiv2019

Charge regulation radically modifies electrostatics in membrane stacks

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, and their number in the stack. Our results shed light on the basic reorganization mechanism of thylakoid membrane stacks.

cond-mat.soft↗

arXiv2018

Electrostatic interaction of particles trapped at fluid interfaces: Effects of geometry and wetting properties

The electrostatic interaction between pairs of spherical or macroscopically long, parallel cylindrical colloids trapped at fluid interfaces is studied theoretically for the case of small inter-particle separations. Starting from the effective interaction between two planar walls and by using the Derjaguin approximation, we address the issue of how the electrostatic interaction between such particles is influenced by their curvatures and by the wetting contact angle at their surfaces. Regarding the influence of curvature, our findings suggest that the discrepancies between linear and nonlinear Poisson-Boltzmann theory, which have been noticed before for planar walls, also occur for spheres and macroscopically long, parallel cylinders, though their magnitude depends on the wetting contact angle. Concerning the influence of the wetting contact angle $θ$ simple relations are obtained for equally sized particles which indicate that the inter-particle force varies significantly with $θ$ only within an interval around $90^\circ$. This interval depends on the Debye length of the fluids and on the size of the particles but not on their shape. For unequally sized particles, a more complicated relation is obtained for the variation of the inter-particle force with the wetting contact angle.

cond-mat.soft↗

arXiv2018

Electrostatic interaction between dissimilar colloids at fluid interfaces

The electrostatic interaction between two non-identical, moderately charged colloids situated in close proximity of each other at a fluid interface is studied. By resorting to a well-justified model system, this problem is analytically solved within the framework of linearized Poisson-Boltzmann (PB) density functional theory (DFT). The resulting interaction comprises a surface and a line part, both of which, as functions of the inter-particle separation, show a rich behavior including monotonic as well as non-monotonic variations. In almost all cases, these variations cannot be captured correctly by using the superposition approximation. Moreover, expressions for the surface tensions, the line tensions and the fluid-fluid interfacial tension, which are all independent of the inter-particle separation, are obtained. Our results are expected to be particularly useful for emulsions stabilized by oppositely charged particles.

cond-mat.soft↗

arXiv2018

Nanoscale Seebeck effect at hot metal nanostructures

We theoretically study the electrolyte Seebeck effect in the vicinity of a heated metal nanostructure, such as the cap of an active Janus colloid in an electrolyte, or gold- coated interfaces in optofluidic devices. The thermocharge accumulated at the surface varies with the local temperature, thus modulating the diffuse part of the electric double layer. On a conducting surface with non-uniform temperature, the isopotential condition imposes a significant polarization charge within the metal. Surprisingly, this does not affect the slip velocity, which takes the same value on insulating and conducting surfaces. Our results for specific-ion effects agree qualitatively with recent observations for Janus colloids in different electrolyte solutions. Comparing the thermal, hydrodynamic, and ion diffusion time scales, we expect a rich transient behavior at the onset of thermally powered swimming, extending to microseconds after switching on the heating.

cond-mat.soft↗

arXiv2018

Spontaneous symmetry breaking of charge-regulated surfaces

The interaction between two chemically identical charge-regulated surfaces is studied using the classical density functional theory. In contrast to common expectations and assumptions, under certain realistic conditions we find a spontaneous emergence of disparate charge densities on the two surfaces. The surface charge densities can differ not only in their magnitude, but quite unexpectedly, even in their sign, implying that the electrostatic interaction between the two chemically identical surfaces can be attractive instead of repulsive. Moreover, an initial symmetry with equal charge densities on both surfaces can also be broken spontaneously upon decreasing the separation between the two surfaces. The origin of this phenomenon is a competition between the adsorption of ions from the solution to the surface and the interaction between the adsorbed ions already on the surface.These findings are fundamental for the understanding of the forces between colloidal objects and, in particular, they are bound to strongly influence the present picture of protein interaction.

cond-mat.soft↗

arXiv2017

Rotational motion of dimers of Janus particles

We theoretically study the motion of a rigid dimer of self-propelling Janus particles. In a simple kinetic approach without hydrodynamic interactions, the dimer moves on a helical trajectory and, at the same time, it rotates about its center of mass. Inclusion of the effects of mutual advection using superposition approximation does not alter the qualitative features of the motion but merely changes the parameters of the trajectory and the angular velocity.

cond-mat.soft↗

arXiv2016

Poisson-Boltzmann study of the effective electrostatic interaction between colloids at an electrolyte interface

The effective electrostatic interaction between a pair of colloids, both of them located close to each other at an electrolyte interface, is studied by employing the full, nonlinear Poisson-Boltzmann (PB) theory within classical density functional theory. Using a simplified yet appropriate model, all contributions to the effective interaction are obtained exactly, albeit numerically. The comparison between our results and those obtained within linearized PB theory reveals that the latter overestimates these contributions significantly at short inter-particle separations. Whereas the surface contributions to the linear and the nonlinear PB results differ only quantitatively, the line contributions show qualitative differences at short separations. Moreover, a dependence of the line contribution on the solvation properties of the two adjacent fluids is found, which is absent within the linear theory. Our results are expected to enrich the understanding of effective interfacial interactions between colloids.

cond-mat.soft↗

arXiv2014

Electrostatic interaction between colloidal particles trapped at an electrolyte interface

The electrostatic interaction between colloidal particles trapped at the interface between two immiscible electrolyte solutions is studied in the limit of small inter-particle distances. Within an appropriate model exact analytic expressions for the electrostatic potential as well as for the surface and line interaction energies are obtained. They demonstrate that the widely used superposition approximation, which is commonly applied to large distances between the colloidal particles, fails qualitatively at small distances and is quantitatively unreliable even at large distances. Our results contribute to an improved description of the interaction between colloidal particles trapped at fluid interfaces.

cond-mat.soft↗

arXiv2014

Thermocharge of a hot spot in an electrolyte solution

We discuss the thermoelectric properties of a locally heated micron-size volume in an electrolyte solution. We find that such a hot spot carries a net charge Q which, for an excess temperature of 10 K, may attain hundreds of elementary charges. The corresponding Seebeck electric field E increases linearly with the radius r inside the heated area, then goes through a maximum, and decays as 1/r2 at larger distances. Our results could be relevant to optothermal actuation of electrolytes and colloidal suspensions.

cond-mat.soft↗

arXiv2014

Collective thermoelectrophoresis of charged colloids

Thermally driven colloidal transport is, to a large extent, due to the thermoelectric or Seebeck effect of the charged solution.We show that, contrary to the generally adopted single-particle picture, the transport coefficient depends on the colloidal concentration. For solutions that are dilute in the hydrodynamic sense, collective effects may significantly affect the thermophoretic mobility. Our results provide an explanation for recent experimental observations on polyelectrolytes and charged particles and suggest that for charged colloids collective behavior is the rule rather than the exception.

cond-mat.soft↗

arXiv2014

Charging of Heated Colloidal Particles Using the Electrolyte Seebeck Effect

We propose a novel actuation mechanism for colloids, which is based on the Seebeck effect of the electrolyte solution: Laser heating of a nonionic particle accumulates in its vicinity a net charge Q, which is proportional to the excess temperature at the particle surface. The corresponding long-range thermoelectric field provides a tool for controlled interactions with nearby beads or with additional molecular solutes. An external field Eext drags the thermocharged particle at a velocity that depends on its size and absorption properties; the latter point could be particularly relevant for separating carbon nanotubes according to their electronic band structure.

cond-mat.soft↗