Charge Distribution on Annealed Polyelectrolytes

Polyelectrolytes such as single and double stranded DNA and many synthetic polymers undergo two structural transitions upon increasing the concentration of multivalent salt or molecules. First, the expanded-stretched chains in low monovalent salt solutions collapse into nearly neutral compact structures when the density of multivalent salt approaches that of the monomers. With further addition of multivalent salt the chains redissolve acquiring expanded-coiled conformations. ...

In this paper we analyze the behavior of hydrophobic polyelectrolytes. It has been proposed that this system adopts a pearl-necklace structure reminiscent of the Rayleigh instability of a charged droplet. Using a Poisson-Boltzmann approach, we calculate the counterion distribution around a given pearl assuming the latter to be penetrable for the counterions. This allows us to calculate the effective electric charge of the pearl as a function of the chemical charge. Our predic...

The collapse of flexible polyelectrolytes in a solution of multivalent counterions is studied by means of a two state model. The states correspond to rod-like and spherically collapsed conformations respectively. We focus on the very dilute monomer concentration regime where the collapse transition is found to occur when the charge of the multivalent salt is comparable (but smaller) to that of the monomers. The main contribution to the free energy of the collapsed conformatio...

We study the behavior of single linear polyelectrolytes condensed by trivalent salt under the action of electric fields through computer simulations. The chain is unfolded when the strength of the electric field is stronger than a critical value. This critical electric field follows a scaling law against chain length and the exponent of the scaling law is $-0.77(1)$, smaller than the theoretical prediction, $-3\nu/2$ [Netz, Phys. Rev. Lett. 90 (2003) 128104], and the one obta...

A living polymers transition is found in molecular dynamics simulations of a charge-symmetric size-asymmetric electrolyte with no anisotropic interactions. The fluid has strong polymeric character at low temperatures, where it consists of large, alternating-charge linear chains and rings in chemical equilibrium. A mean-field theory of chain association is consistent with the existence of such a transition. In the polymeric phase the system is very weakly conducting or electri...

Stretching dynamics of polymers in microfluidics is of particular interest for polymer scientists. As a charged polymer, a polyelectrolyte can be deformed from its coiled equilibrium configuration to an extended chain by applying uniform or non-uniform electric fields. By means of hybrid lattice Boltzmann-molecular dynamics simulations, we investigate how the condensed counterions around the polyelectrolyte contribute to the polymer stretching in inhomogeneous fields. As an a...

The adsorption of highly \textit{oppositely} charged flexible polyelectrolytes (PEs) on a charged planar substrate is investigated by means of Monte Carlo (MC) simulations. We study in detail the equilibrium structure of the first few PE layers. The influence of the chain length and of a (extra) non-electrostatic short range attraction between the polycations and the negatively charged substrate is considered. We show that the stability as well as the microstructure of the PE...

The effective elasticity of highly charged stiff polyelectrolytes is studied in the presence of counterions, with and without added salt. The rigid polymer conformations may become unstable due to an effective attraction induced by counterion density fluctuations. Instabilities at the longest, or intermediate length scales may signal collapse to globule, or necklace states, respectively. In the presence of added-salt, a generalized electrostatic persistence length is obtained...

The persistence length of a single, strongly charged, stiff polyelectrolyte chain is investigated theoretically. Path integral formulation is used to obtain the effective electrostatic interaction between the monomers. We find significant deviations from the classical Odijk, Skolnick and Fixman (OSF) result. An induced attraction between monomers is due to thermal fluctuations and correlations between bound counterions. The electrostatic persistence length is found to be smal...

We study theoretically using scaling arguments the behavior of polyelectrolyte gels in poor solvents. Following the classical picture of Katchalsky, our approach is based on single chain elasticity but it accounts for the recently proposed pearl-necklace structure of polyelectrolytes in poor solvents. The elasticity both of gels at swelling equilibrium and of partially swollen, non equilibrium, gels is studied when parameters such as the ionic strength or the fraction of char...