Inverted critical adsorption of polyelectrolytes in confinement

What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer-surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density $\sigma_c$-defining the adsorption-desorption transition-are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of $\sigma_c$ for the concave interfaces versus the Debye screening length $1/\kappa$ and the extent of confinement $a$ for these three interfaces for small $\kappa a$ values. For large $\kappa a$ the critical adsorption condition approaches the planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness $a$ is of the order of $1/\kappa$. We also rationalize how $\sigma_c(\kappa)$ gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length onto critical adsorption-the effect often hard to tackle theoretically-putting an emphasis on polymers inside attractive spherical cavities.Comment: 12 pages, 10 figures, RevTe

Non-linear Poisson-Boltzmann Theory for Swollen Clays

The non-linear Poisson-Boltzmann equation for a circular, uniformly charged platelet, confined together with co- and counter-ions to a cylindrical cell, is solved semi-analytically by transforming it into an integral equation and solving the latter iteratively. This method proves efficient, robust, and can be readily generalized to other problems based on cell models, treated within non-linear Poisson-like theory. The solution to the PB equation is computed over a wide range of physical conditions, and the resulting osmotic equation of state is shown to be in fair agreement with recent experimental data for Laponite clay suspensions, in the concentrated gel phase.Comment: 13 pages, 4 postscript figure

Structure of trajectories of complex matrix eigenvalues in the Hermitian-non-Hermitian transition

The statistical properties of trajectories of eigenvalues of Gaussian complex matrices whose Hermitian condition is progressively broken are investigated. It is shown how the ordering on the real axis of the real eigenvalues is reflected in the structure of the trajectories and also in the final distribution of the eigenvalues in the complex plane.Comment: 12 pages, 3 figure

Critical adsorption of polyelectrolytes onto charged Janus nanospheres

Based on extensive Monte Carlo simulations and analytical considerations we study the electrostatically driven adsorption of flexible polyelectrolyte chains onto charged Janus nanospheres. These net-neutral colloids are composed of two equally but oppositely charged hemispheres. The critical binding conditions for polyelectrolyte chains are analysed as function of the radius of the Janus particle and its surface charge density, as well as the salt concentration in the ambient solution. Specifically for the adsorption of finite-length polyelectrolyte chains onto Janus nanoparticles, we demonstrate that the critical adsorption conditions drastically differ when the size of the Janus particle or the screening length of the electrolyte are varied. We compare the scaling laws obtained for the adsorption-desorption threshold to the known results for uniformly charged spherical particles, observing significant disparities. We also contrast the changes to the polyelectrolyte chain conformations and the binding energy distributions close to the adsorption-desorption transition for Janus nanoparticles to those for simple spherical particles. Finally, we discuss experimentally relevant physico-chemical systems for which our simulations results may become important. In particular, we observe similar trends with polyelectrolyte complexation with oppositely but heterogeneously charged proteins.Comment: 13 pages, 11 figures, RevTeX

The Role of Fermions in Bubble Nucleation

We present a study of the role of fermions in the decay of metastable states of a scalar field via bubble nucleation. We analyze both one and three-dimensional systems by using a gradient expansion for the calculation of the fermionic determinant. The results of the one-dimensional case are compared to the exact results of previous work.Comment: 15 pages, revtex, 9 figure

Power-law statistics and stellar rotational velocities in the Pleiades

In this paper we will show that, the non-gaussian statistics framework based on the Kaniadakis statistics is more appropriate to fit the observed distributions of projected rotational velocity measurements of stars in the Pleiades open cluster. To this end, we compare the results from the $\kappa$ and $q$-distributions with the Maxwellian.Comment: 13 pages, 3 figure