arXiv subjects

I. Borukhov

Publications and source records attributed to I. Borukhov.

9 recordsLinked to original sources

arXiv2002

Raft Instability of Biopolymer Gels

Following recent X-ray diffraction experiments by Wong, Li, and Safinya on biopolymer gels, we apply Onsager excluded volume theory to a nematic mixture of rigid rods and strong ``$π/2$'' cross-linkers obtaining a long-ranged, highly anisotropic depletion attraction between the linkers. This attraction leads to breakdown of the percolation theory for this class of gels, to breakdown of Onsager's second-order virial method, and to formation of heterogeneities in the form of raft-like ribbons.

cond-mat.soft↗

arXiv2001

Elastically-Driven Linker Aggregation between Two Semi-Flexible Polyelectrolytes

The behavior of mobile linkers connecting two semi-flexible charged polymers, such as polyvalent counterions connecting DNA or F-actin chains, is studied theoretically. The chain bending rigidity induces an effective repulsion between linkers at large distances while the inter-chain electrostatic repulsion leads to an effective short range inter-linker attraction. We find a rounded phase transition from a dilute linker gas where the chains form large loops between linkers to a dense disordered linker fluid connecting parallel chains. The onset of chain pairing occurs within the rounded transition.

cond-mat.soft↗

arXiv2000

Polyelectrolyte Titration: Theory and Experiment

Titration of methacrylic acid / ethyl-acrylate copolymers is studied experimentally and theoretically. At low salt concentrations, this polyacid exhibits a plateau in the titration curve below the neutralization point. The plateau has been often attributed to a first-order phase transition associated with polymer conformational changes. We argue that the specific shape of titration curves of hydrophobic polyelectrolytes is due to electrostatics and does not necessarily require a conformation change of the polyelectrolyte chains. We calculate the free energy at the mean-field level and its first-order (one loop) correction using a loop expansion. The latter is dominated by Debye-Huckel--like charge-charge correlations as well as by correlations between dissociation sites along the polymer chain. We show that the one-loop corrections to the free energy lead to titration curves that agree with experiments. In particular, the model explains the decrease of the pH at the plateau when the polymer concentration is increased or when salt is added to the solution.

cond-mat.soft↗

arXiv2000

Stabilizing Grafted Colloids in a Polymer Melt: Favorable Enthalpic Interactions

The interactions between spherical colloids covered with end-grafted polymers (brushes) immersed in a polymer melt are studied theoretically. We show that attractive enthalpic interactions between the two polymer species, characterized by a negative Flory parameter (chi<0), can stabilize the colloidal dispersion. The stabilizing mechanism is a result of a structural change from a dry brush, where the melt chains do not penetrate deeply into the brush, to a wet brush, where the free chains penetrate the brush and force the grafted chains to extend into the melt.

cond-mat.soft↗

arXiv1999

Adsorption of Large Ions from an Electrolyte Solution: A Modified Poisson-Boltzmann Equation

The behavior of electrolyte solutions close to a charged surface is studied theoretically. A modified Poisson-Boltzmann equation which takes into account the volume excluded by the ions in addition to the electrostatic interactions is presented. In a formal lattice gas formalism the modified Poisson-Boltzmann equation can be obtained from a mean-field approximation of the partition function. In an alternative phenomenological approach, the same equation can be derived by including the entropy of the solvent molecules in the free energy. In order to visualize the effect of the steric repulsion, a simple case of a single, highly charged, flat surface is discussed. This situation resembles recent adsorption experiments of large ions onto a charged monolayer. A simple criterion for the importance of the steric effects is expressed in terms of the surface charge density and the size of the ions. It is shown that when these effects are important a saturated layer is formed near the surface. A modified Grahame equation relating the ion concentration at the surface to the surface charge density is obtained.

cond-mat.soft↗

arXiv1998

Random Polyelectrolytes and Polyampholytes in Solution

The behavior of polyelectrolytes and polyampholytes in semi-dilute solutions is investigated theoretically. Various statistical charge distributions along the polyelectrolyte chains are considered: smeared, annealed, permuted and quenched. Annealed polyampholytes are also considered. Path integral formulation was used to derive mean field free energies for the different models. Self-consistent field equation is obtained for the polymer order parameter and a Poisson-Boltzmann like equation for the electrostatic potential. The random phase approximation is used to calculate the monomer-monomer structure factor S(q) for the different statistical charge distribution models. We show that in the annealed model, fluctuations of the the monomer charges contribute to the electrostatic screening in addition to the free ions in the solution. The strength of this screening depends on the variance of the monomer charge distribution and is especially important for polyampholytes in bad solvent conditions where the mesophase separation is enhanced. The ratio between the variance and the net average charge determines whether polyampholytes behave as polyelectrolytes or as neutral chains.

cond-mat.soft↗

arXiv1998

The Effect of Polyelectrolyte Adsorption on Inter-Colloidal Forces

The behavior of polyelectrolytes between charged surfaces immersed in semi-dilute solutions is investigated theoretically. A continuum mean field approach is used for calculating numerically concentration profiles between two electrodes held at a constant potential. A generalized contact theorem relates the inter-surface forces to the concentration profiles. The numerical results show that over-compensation of the surface charges by adsorbing polyelectrolytes can lead to effective attraction between equally charged surfaces. Simple scaling arguments enable us to characterize qualitatively the inter-surface interactions as function of the fraction of charged monomers p and the salt concentration c_b. In the low salt regime we find strong repulsion at short distances, where the polymers are depleted from the inter-surface gap, followed by strong attraction when the two adsorbed layers overlap. The magnitude of this attraction scales as p^{1/2} and its dominant length scale is proportional to a/p^{1/2}, where a is the monomer size. At larger distances the two adsorbing surfaces interact via a weak electrostatic repulsion. For strong polyelectrolytes at high salt concentration the polymer contribution to attraction at short distances scales as p/c_b^{1/2} and the length scale is proportional to kappa*a^2/p, where kappa^{-1} is the Debye-Huckel screening length. For weak polyelectrolytes at high salt concentration the interaction is repulsive for all surface separations and decays exponentially with a decay length equal to kappa^{-1}. The effect of irreversible adsorption is discussed as well and it is shown that inter-surface attraction can be obtained in this case as well.

cond-mat.soft↗

arXiv1998

Steric Effects in Electrolytes: A Modified Poisson-Boltzmann Equation

The adsorption of large ions from solution to a charged surface is investigated theoretically. A generalized Poisson--Boltzmann equation, which takes into account the finite size of the ions is presented. We obtain analytical expressions for the electrostatic potential and ion concentrations at the surface, leading to a modified Grahame equation. At high surface charge densities the ionic concentration saturates to its maximum value. Our results are in agreement with recent experiments.

cond-mat.soft↗

arXiv1997

Scaling Laws of Polyelectrolyte Adsorption

Adsorption of charged polymers (polyelectrolytes) from a semi-dilute solution to a charged surface is investigated theoretically. We obtain simple scaling laws for (i) the amount of polymer adsorbed to the surface, Gamma, and (ii) the width of the adsorbed layer D, as function of the fractional charge per monomer p and the salt concentration c_b. For strongly charged polyelectrolytes (p<1) in a low-salt solution, both Gamma and D scale as p^{-1/2}. In salt-rich solutions D~c_b^{1/2}/p whereas the scaling behavior of Gamma depends on the strength of the polymer charge. For weak polyelectrolytes (p<<1) we find that Gamma~p/c_b^{1/2} while for strong polyelectrolytes Gamma~c_b^{1/2}/p. Our results are in good agreement with adsorption experiments and with numerical solutions of mean-field equations.

cond-mat.soft↗