Polyelectrolytes Adsorption: Chemical and Electrostatic Interactions

Mean-field theory is used to model polyelectrolyte adsorption and the possibility of overcompensation of charged surfaces. For charged surfaces that are also chemically attractive, the overcharging is large in high salt conditions, amounting to 20-40% of the bare surface charge. However, full charge inversion is not obtained in thermodynamical equilibrium for physical values of the parameters. The overcharging increases with addition of salt, but does not have a simple scaling form with the bare surface charge. Our results indicate that more evolved explanation is needed in order to understand polyelectrolyte multilayer built-up. For strong polymer-repulsive surfaces, we derive simple scaling laws for the polyelectrolyte adsorption and overcharging. We show that the overcharging scales linearly with the bare surface charge, but its magnitude is very small in comparison to the surface charge. In contrast with the attractive surface, here the overcharging is found to decrease substantially with addition of salt. In the intermediate range of weak repulsive surfaces, the behavior with addition of salt crosses over from increasing overcharging (at low ionic strength) to decreasing one (at high ionic strength). Our results for all types of surfaces are supported by full numerical solutions of the mean-field equations.Comment: 17 pages, 7 figures, final version. to be published in PR

Fluctuation-dissipation relation and stationary distribution for an exactly solvable many-particle model far from equilibrium

An exactly solvable, Hamiltonian-based model of many massive particles that are coupled by harmonic potentials and driven by stochastic non-equilibrium forces is introduced. The stationary distribution as well as the fluctuation-dissipation relation are derived in closed form for the general non-equilibrium case. Deviations from equilibrium are on one hand characterized by the difference of the obtained stationary distribution from the Boltzmann distribution, which is possible because the model derives from a particle Hamiltonian. The difference between the obtained non-equilibrium fluctuation-dissipation relation and the standard equilibrium fluctuation-dissipation theorem allows to quantify non-equilibrium in an alternative fashion. Both indicators of non-equilibrium behavior, i.e. deviations from the Boltzmann distribution and deviations from the equilibrium fluctuation-dissipation theorem, can be expressed in terms of a single non-equilibrium parameter \alpha that involves the ratio of friction coefficients and random force strengths. The concept of a non-equilibrium effective temperature, which can be defined by the relation between fluctuations and the dissipation, is by comparison with the exactly derived stationary distribution shown not to hold, even if the effective temperature is made frequency dependent. The analysis is not confined to close-to-equilibrium situations but rather is exact and thus holds for arbitrarily large deviations from equilibrium. Also, the suggested harmonic model can be obtained from non-linear mechanical network systems by an expansion in terms of suitably chosen deviatory coordinates, the obtained results should thus be quite general. This is demonstrated by comparison of the derived non-equilibrium fluctuation dissipation relation with experimental data on actin networks that are driven out of equilibrium by energyconsuming protein motors. The comparison is excellent and allows to extract the non-equilibrium parameter \alpha from experimental spectral response and fluctuation data

Surface states in nearly modulated systems

A Landau model is used to study the phase behavior of the surface layer for magnetic and cholesteric liquid crystal systems that are at or near a Lifshitz point marking the boundary between modulated and homogeneous bulk phases. The model incorporates surface and bulk fields and includes a term in the free energy proportional to the square of the second derivative of the order parameter in addition to the usual term involving the square of the first derivative. In the limit of vanishing bulk field, three distinct types of surface ordering are possible: a wetting layer, a non-wet layer having a small deviation from bulk order, and a different non-wet layer with a large deviation from bulk order which decays non-monotonically as distance from the wall increases. In particular the large deviation non-wet layer is a feature of systems at the Lifshitz point and also those having only homogeneous bulk phases.Comment: 6 pages, 7 figures, submitted to Phys. Rev.

Multiple surface wave solutions on linear viscoelastic media

We study the generic dispersion relation of surface waves on a semi-infinite viscoelastic medium bounded by a 2D viscoelastic interface, including the effects of gravitation, surface tension and bending rigidity. The classical Rayleigh, capillary-gravity and Lucassen wave solutions result as limiting cases. We identify an additional solution that differs from all previously described waves in that gravitation, surface tension and bulk shear viscosity must simultaneously be nonzero, and which exists on a pure air-water interface. For a surfactant monolayer on water, the number of coexisting wave solutions switches between one and three, depending on interfacial compressibility and frequency

Histogram Monte Carlo study of next-nearest-neighbor Ising antiferromagnet on a stacked triangular lattice

Critical properties of the Ising model on a stacked triangular lattice, with antiferromagnetic first and second-neighbor in-plane interactions, are studied by extensive histogram Monte Carlo simulations. The results, in conjunction with the recently determined phase diagram, strongly suggest that the transition from the period-3 ordered state to the paramagnetic phase remains in the xy universality class. This conclusion is in contrast with a previous suggestion of mean-field tricritical behavior.Comment: 13 pages (RevTex 3.0), 10 figures available upon request, CRPS-93-0

Cyclization dynamics of finite-length collapsed self-avoiding polymers

We study the end-point cyclization of ideal and interacting polymers as a function of chain length N. For the cyclization time �cyc of ideal chains we recover the known scaling �cyc � N2 for different backbone models, for a self-avoiding slightly collapsed chain we obtain from Langevin simulations and scaling theory a modified scaling �cyc � N5=3. By extracting the memory kernel that governs the non-Markovian end-point kinetics, we demonstrate that the dynamics of a finite-length collapsed chain is dominated by the crossover between swollen and collapsed behavior

Unfolding and Folding Internal Friction of β‑Hairpins Is Smaller than That of α‑Helices

By the forced unfolding of polyglutamine and polyalanine homopeptides in competing α-helix and β-hairpin secondary structures, we disentangle equilibrium free energetics from nonequilibrium dissipative effects. We find that α-helices are characterized by larger friction or dissipation upon unfolding, regardless of whether they are free energetically preferred over β-hairpins or not. Our analysis, based on MD simulations for atomistic peptide models with explicit water, suggests that this difference is related to the internal friction and mostly caused by the different number of intrapeptide hydrogen bonds in the α-helix and β-hairpin states

The Persistence Length of a Strongly Charged, Rod-like, Polyelectrolyte in the Presence of Salt

The persistence length of a single, intrinsically rigid polyelectrolyte chain, above the Manning condensation threshold is investigated theoretically in presence of added salt. Using a loop expansion method, the partition function is consistently calculated, taking into account corrections to mean-field theory. Within a mean-field approximation, the well-known results of Odijk, Skolnick and Fixman are reproduced. Beyond mean-field, it is found that density correlations between counterions and thermal fluctuations reduce the stiffness of the chain, indicating an effective attraction between monomers for highly charged chains and multivalent counterions. This attraction results in a possible mechanical instability (collapse), alluding to the phenomenon of DNA condensation. In addition, we find that more counterions condense on slightly bent conformations of the chain than predicted by the Manning model for the case of an infinite cylinder. Finally, our results are compared with previous models and experiments.Comment: 13 pages, 2 ps figure

Adhesion-induced phase separation of multiple species of membrane junctions

A theory is presented for the membrane junction separation induced by the adhesion between two biomimetic membranes that contain two different types of anchored junctions (receptor/ligand complexes). The analysis shows that several mechanisms contribute to the membrane junction separation. These mechanisms include (i) the height difference between type-1 and type-2 junctions is the main factor which drives the junction separation, (ii) when type-1 and type-2 junctions have different rigidities against stretch and compression, the ``softer'' junctions are the ``favored'' species, and the aggregation of the softer junction can occur, (iii) the elasticity of the membranes mediates a non-local interaction between the junctions, (iv) the thermally activated shape fluctuations of the membranes also contribute to the junction separation by inducing another non-local interaction between the junctions and renormalizing the binding energy of the junctions. The combined effect of these mechanisms is that when junction separation occurs, the system separates into two domains with different relative and total junction densities.Comment: 23 pages, 6 figure