Self-similarity of nonlinear screening in asymmetric complex plasmas

In this paper, two-component electroneutral systems of finite-sized macroions and oppositely charged point-like microions in the average spherical electroneutral Wigner–Seitz cell with a central macroion are studied. We investigate the self-similarity of nonlinear screening of highly charged macroions by microions in a classical asymmetrically charged complex plasma. This work is devoted to the problem of the relationship between the effective (‘visible’) charge of the macroion Z^* and its initial charge Z taking into account the effect of the nonlinear screening. It is analysed how the form of the dependence Z^*(Z) changes. The self-similarity of this dependence has been demonstrated for various characteristic system temperatures, macroion concentrations, and macroion sizes.     

Effect of the non‐linear screening on a modification of the Debye–Hückel plus hole approximation in complex plasma

The authors analyse two‐component electroneutral systems of classical macroions of finite size and point‐like oppositely charged microions. This article deals with the modification of the Debye–Hückel plus hole approximation when a non‐linear screening effect is taken into account in a complex plasma. Parameters of non‐linear screening of the macroions by surrounding microions are calculated within the framework of the Poisson–Boltzmann approximation. Two effects are found as a result of such calculations: (a) subdivision of all microions into two subclasses, free microions and bound microions and (b) a significant reduction of an effective charge Z^* of the macroion in comparison with its true value Z due to the non‐linear screening by a thin high‐density envelope of the bound microions. We show that the value of a non‐ideal portion of an internal energy differs considerably in the case when the non‐linear screening effect is taken into account in the vicinity of the macroion.     

General solvation motifs of a charged linear macroion in an aqueous droplet

ABSTRACT

We explore the solvation patterns of a charged rigid and semi-rigid linear macroion in an aqueous droplet. The solvation patterns are summarised in an empirical ‘phase diagram’ on the parameter space defined by the length of the macroion and its charge density. In the study, we employ molecular dynamics and atomistic modelling. The macroion is represented by a positively charged carbon nanotube. Linear macroion-solvent interactions in droplets are distinct from those of spherical ions because of the interplay among several factors such as the tendency of the solvent to form spherical droplets in order to minimise the surface energy, the constraint on the charge of a spherical droplet imposed by the Rayleigh limit, the solvation energy of the macroion and its length. The combination of all these factors may lead to a variety of solvent distributions along the rigid rod such as asymmetric solvation of the linear macroion, formation of spiky ‘star’-like distribution of solvent, partial wetting of the rod by a droplet. The study provides insight into the solvation of macroions in droplets with applications in electrosprayed macroions and atmospheric aerosols. We also propose a possible path of generating a sequence of nanoparticles of different shapes (spheres, multi-point stars) along a linear macromolecule by exploiting the various solvation patterns.     

Bending of charged flexible membranes due to the presence of macroions

We investigate the bending of flexible charged membranes due to the presence of rigid rodlike macroions in the framework of the Debye-Hückel approximation. When the macroions are fixed in space at some distance from the bilayer the membrane bends towards them; we calculate the exact deformation profile. On the other hand a macroion which is adsorbed on the membrane causes a deflection of the bilayer. Finally, we consider swollen lamellar polyanion/charged-lipid complexes where the macroions are intercalated between charged lipid bilayers. We predict the occurrence of a double adsorption (pinching effect) of the macroion for sufficiently flexible membranes. Received: 9 February 1998 / Revised: 9 June 1998 / Accepted: 2 July 1998     

Strong attraction between charged spheres due to metastable ionized states

We report a mechanism which can lead to long-range attractions between like-charged spherical macroions, stemming from the existence of metastable ionized states. We show that the ground state of a single highly charged colloid plus a few excess counterions is overcharged. For the case of two highly charged macroions in their neutralizing divalent counterion solution we demonstrate that, in the regime of strong Coulomb coupling, the counterion clouds are very likely to be unevenly distributed, leading to one overcharged and one undercharged macroion. This long-living metastable configuration in turn leads to a long-range Coulomb attraction.     

Salt-modulated structure of polyelectrolyte-macroion complex fibers

The structure and stability of strongly charged complex fibers, formed by complexation of a single long semi-flexible polyelectrolyte chain and many oppositely charged spherical macroions, are investigated numerically at the ground-state level using a chain-sphere cell model. The model takes into account chain elasticity as well as electrostatic interactions between charged spheres and chain segments. Using a numerical optimization method based on a periodically repeated unit cell, we obtain fiber configurations that minimize the total energy. The optimal fiber configurations exhibit a variety of helical structures for the arrangement of macroions including zig-zag, solenoidal and beads-on-a-string patterns. These structures result from the competition between attraction between spheres and the polyelectrolyte chain (which favors chain wrapping around the spheres), chain bending rigidity and electrostatic repulsion between chain segments (which favor unwrapping of the chain), and the interactions between neighboring sphere-chain complexes which can be attractive or repulsive depending on the system parameters such as salt concentration, macroion charge and chain length per macroion (linker size). At about physiological salt concentration, dense zig-zag patterns are found to be energetically most stable when parameters appropriate for the DNA-histone system in the chromatin fiber are adopted. In fact, the predicted fiber diameter in this regime is found to be around 30 nanometers, which roughly agrees with the thickness observed in in vitro experiments on chromatin. We also find a macroion (histone) density of 5–6 per 11nm which agrees with results from the zig-zag or cross-linker models of chromatin. Since our study deals primarily with a generic chain-sphere model, these findings suggest that structures similar to those found for chromatin should also be observable for polyelectrolyte-macroion complexes formed in solutions of DNA and synthetic nano-colloids of opposite charge. In the ensemble where the mean linear density of spheres on the chain is fixed, the present model predicts a phase separation at intermediate salt concentrations into a densely packed complex phase and a dilute phase.     

Macroion-induced compositional instability of binary fluid membranes

Macroion adsorption on a mixed, fluid, lipid membrane containing oppositely charged lipids induces local changes in lipid composition at the interaction zones, and gradients at their boundaries. Including these effects in the free energy of the macroion-dressed membrane we derive its spinodal equation, and show that nonideal lipid mixing can lead to (lipid-mediated) attraction between macroions and lateral phase separation in the composite membrane. The critical nonideality for this transition is substantially smaller than that of the bare lipid membrane, decreasing with macroion size and charge. That is, the lipid membrane is destabilized by macroion adsorption.     

Mayer function perturbation theory of effective interaction of charged colloids

In this paper, the effective interaction between charged colloids has been studied based on the standard Mayer function perturbation theory. With the formalism developed in this paper, the effective interaction as a function of Mayer functions and the correlation functions of the homogeneous microions is obtained. The asymptotic behaviour of the effective interaction at large distance is analysed in detail. It is found that at large distance the effective interaction is Yukawa like, provided the bare charge is replaced by the renormalised one. Exact expressions for the renormalised charge and the decay length as functions of the short-range part of the Mayer function and that of the correlation function of the homogeneous microions are obtained. With perturbation methods, it is easy to see how the effective interaction at large distance is affected by microion correlations and nonlinearity.     

Solvent and nonlinear effects on the charge renormalization of nanoparticles within a molecular electrolyte model

A general analysis of the effect of the molecular structure of a polar solvent on the effective interactions among suspended charged nanoparticles (macroions up to 30 nm in size) is performed using a simple molecular model for the solvent in the supporting electrolyte. The solvent molecules are modeled as small rods with end point charges of opposite sign and equal magnitude, whereas the small ions are assumed to be point-like. We compare the renormalized charges of the effective pair potentials (EPPs) among the spherical nanoparticles, obtained after contracting the supporting electrolyte, with those obtained from a similar model, which does not include the solvent molecules. The parameters of both models have been adjusted to give the same screening length. The comparison shows that the renormalized charges are overestimated when the molecular structure of the solvent is neglected. This is in agreement with the image charge effect induced by the different permittivities inside and outside the nanoparticles for the model with explicit solvent molecules; an effect that is missing in the model without solvent molecules. A new numerical method allows us to explore macroion diameters much larger than the solvent molecular size.     

The distribution of counterions around synthetic rod-like polyelectrolytes in solution

An investigation of the radial distribution of the counterions of a synthetic rodlike polyelectrolyte in aqueous solution is presented. The cationic polyelectrolyte used here has a poly(p-phenylene) backbone. For typical molecular weights the macroion comprises approximately one persistence length (ca. 20 nm) and effects of finite stiffness may be disregarded. Each repeating unit bears four charges which leads to a charge parameter of ξ = 6.65. The distribution of the iodide counterions around this highly charged macroion is studied by small-angle X-ray scattering (SAXS) in dilute aqueous solution. These investigations are supplemented by measurements using anomalous small-angle X-ray scattering (ASAXS) that furnishes additional information about the contrast of the macroion. Data taken at high scattering angles give indication for contributions caused by the longitudinal fluctuations of the counterions. After correction for this effect the experimental results are compared to intensities calculated by use of the Poisson-Boltzmann (PB)-cell model. It is found that the PB-cell model describes the corrected data at intermediate and high scattering angles. Deviations at low scattering angle are attributed to the mutual interaction of the rod-like polyelectrolyte that can be described in terms of an effective structure factor. Data taken at lowest scattering angles point to a weak attraction between the rod-like macroions. Received: 27 July 2001 and Received in final form 27 March 2002     

The Laplace transform of the MSA pair distribution functions between macroions in an ion-dipole fluid

The Laplace transform is obtained for the pair distribution function between a pair of ions, an ion and a macroion, and a pair of macroions in an ion-dipole fluid. This fluid is a simplified model of an electrolyte with a discrete model of solvent (hard spheres with embedded point dipoles). From these results, an expression for the solvation force between macroions is obtained. This result consists of the classical DLVO result plus a series of corrections.     

Macroions in salty water with multivalent ions: giant inversion of charge

Screening of a strongly charged macroion by oppositely charged colloidal particles, micelles, or short polyelectrolytes is considered. Because of strong lateral repulsion such multivalent counterions form a strongly correlated liquid at the surface of the macroion. This liquid provides correlation-induced attraction of multivalent counterions to the macroion surface. As a result even a moderate concentration of multivalent counterions in the solution inverts the sign of the net macroion charge. We show that at high concentration of monovalent salt the absolute value of inverted charge can be larger than the bare one. This giant inversion of charge can be observed in electrophoresis.     

Dielectrophoresis of nanocolloids: A molecular dynamics study

Dielectrophoresis (DEP), the motion of polarizable particles in non-uniform electric fields, has become an important tool for the transport, separation, and characterization of microparticles in biomedical and nanoelectronics research. In this article we present, to our knowledge, the first molecular dynamics simulations of DEP of nanometer-sized colloidal particles. We introduce a simplified model for a polarizable nanoparticle, consisting of a large charged macroion and oppositely charged microions, in an explicit solvent. The model is then used to study DEP motion of the particle at different combinations of temperature and electric field strength. In accord with linear response theory, the particle drift velocities are shown to be proportional to the DEP force. Analysis of the colloid DEP mobility shows a clear time dependence, demonstrating the variation of friction under non-equilibrium. The time dependence of the mobility further results in an apparent weak variation of the DEP displacements with temperature.     

To what extent of ion neutralization can multivalent ion distributions around RNA-like macroions be described by Poisson-Boltzmann theory?

Nucleic acids are negatively charged biomolecules, and metal ions in solutions are important to their folding structures and thermodynamics, especially multivalent ions. However, it has been suggested that the binding of multivalent ions to nucleic acids cannot be quantitatively described by the well-established Poisson-Boltzmann(PB) theory. In this work, we made extensive calculations of ion distributions around various RNA-like macroions in divalent and trivalent salt solutions by PB theory and Monte Carlo(MC) simulations. Our calculations show that PB theory appears to underestimate multivalent ion distributions around RNA-like macroions while can reliably predict monovalent ion distributions. Our extensive comparisons between PB theory and MC simulations indicate that when an RNA-like macroion gets ion neutralization beyond a "critical" value, the multivalent ion distribution around that macroion can be approximately described by PB theory.Furthermore, an empirical formula was obtained to approximately quantify the critical ion neutralization for various RNAlike macroions in multivalent salt solutions, and this empirical formula was shown to work well for various real nucleic acids including RNAs and DNAs.     

Simple approach for charge renormalization in highly charged macroions

We revisit the notion of renormalized charge, which is a concept of central importance in the field of highly charged colloidal or polyelectrolyte solutions. Working at the level of a linear Debye-Hückel-like theory only, we propose a versatile method to predict the saturated amount of charge renormalization, which is, however, a nonlinear effect arising at strong electrostatic coupling. The results are successfully tested against nonlinear Poisson-Boltzmann theory for polyions of various shapes (planar, cylindrical, and spherical), both in the infinite dilution limit or in confined geometry, with or without added electrolyte. Our approach, accurate for monovalent microions in solvents such as water, is finally confronted against experimental results on charged colloids and B-DNA solutions.     

Rescaled mean spherical approximation structure factor for an aqueous suspension of polystyrene spheres

Rescaled mean spherical approximation (RMSA) has been used to calculate the structure factor for the aqueous suspension of polystyrene macroions with the interaction potential taken according to Derjaguin and Landau (1941) and Verwey and Overbeek (1948) (DLVO) model. The effects of charge over the macroion and size on the surface potential and therefore, the structure factor have been studied. The breakdown of the DLVO potential with an excess charge over the macroion (⩾800e) has been reported. The oscillation in the first peak height of structure factor versus wave vector curve with size has been correlated with the Debye length.     

Non-monotonic swelling of a macroion due to correlation-induced charge inversion

It is known that a large, charged body immersed in a solution of multivalent counterions may undergo charge inversion as the counterions adsorb to its surface. We use the theory of charge inversion to examine the case of a deformable, porous macroion which may adsorb multivalent ions into its bulk to form a three-dimensional strongly-correlated liquid. This adsorption may lead to non-monotonic changes in the size of the macroion as multivalent ions are added to the solution. The macroion first shrinks as its bare charge is screened and then reswells as the adsorbed ions invert the sign of the net charge. We derive a value for the outward pressure experienced by such a macroion as a function of the ion concentration in solution. We find that for small deviations in the concentration of multivalent ions away from the neutral point (where the net charge of the body is zero), the swollen size grows parabolically with the logarithm of the ratio of multivalent ion concentration to the concentration at the neutral point.     

Electrophoresis of a charge-inverted macroion complex: Molecular-dynamics study

We have performed molecular-dynamics simulations to study the effect of an external electric field on a macroion in the solution of multivalent Z : 1 salt. To obtain plausible hydrodynamics of the medium, we explicitly make the simulation of many neutral particles along with ions. In a weak electric field, the macroion drifts together with the strongly adsorbed multivalent counterions along the electric field, in the direction proving inversion of the charge sign. The reversed mobility of the macroion is insensitive to the external field, and increases with salt ionic strength. The reversed mobility takes a maximal value at intermediate counterion valence. The motion of the macroion complex does not induce any flow of the neutral solvent away from the macroion, which reveals screening of hydrodynamic interactions at short distances in electrolyte solutions. A very large electric field, comparable to the macroion unscreened field, disrupts charge inversion by stripping the adsorbed counterions off the macroion. Received 5 December 2001 and Received in final form 10 April 2002     

The interaction of classical Yang-Mills charges

Beginning with Khriplovich's formulation of the two point charge Yang-Mills problem, the gauge freedom is used to reduce by one the number of quantities entering the field equations. While a Coulomb solution is shown to exist for any orientation of the color charges, any solution which has a magnetic field present will have lower energy. When the field equations are solved for the simple charge configurations of parallel plates and cylindrical capacitors, one finds screening due to the vector potential. This screening is shown to be complete for any isolated charged plate or line charge. This result may be an indication that isolated charge cannot occur physically for the classical Yang-Mills theory.     

Comparison of structure factors and pair correlation functions obtained using coulomb attractive potential and screened coulomb potential for the suspended macroions

The structure factors and pair correlation functions have been calculated for the macroions suspended in water using coulomb attractive potential (CAP) and the results have been compared well with the results obtained from the RMSA and MMSA using screened coulomb potential (SCP). Differences among the values of compressibility in the limit of zero momentum transfer, excess energy per macroion and coordination number for both the potentials have been reported. Liquid like ordering of the FCC type has been obtained using both CAP as well as SCP potentials between suspended macroions.