Universal reduction of pressure between charged surfaces by long-wavelength surface charge modulation

We predict theoretically that long-wavelength surface charge modulations universally reduce the pressure between the charged surfaces with counterions compared with the case of uniformly charged surfaces with the same average surface charge density. The physical origin of this effect is the fact that surface charge modulations always lead to enhanced counterion localization near the surfaces, and hence, fewer charges at the midplane. We confirm the last prediction with Monte Carlo simulations.Comment: 8 pages 1 figure, Europhys. Lett., in pres

Charge localization in multiply charged clusters and their electrical properties: Some insights into electrospray droplets

The surface composition of charged Lennard-Jones clusters A$_N^{n+}$, composed of N particles (55 \leq N \leq 1169) among which n are positively charged with charge q, thus having a net total charge Q = nq, is investigated by Monte Carlo with Parallel Tempering simulations. At finite temperature, the surface sites of these charged clusters are found to be preferentially occupied by charged particles carrying large charges, due to Coulombic repulsions, but the full occupancy of surface sites is rarely achieved for clusters below the stability limit defined in this work. Large clusters (N = 1169) follow the same trends, with a smaller propensity for positive particles to occupy the cluster surface at non-zero temperature. We show that these charged clusters rather behave as electrical spherical conductors for the smaller sizes (N \leq 147) but as spheres uniformly charged in their volume for the larger sizes (N = 1169).Comment: 10 pages and 4 figure

Sorption and spatial distribution of protein globules in charged hydrogel particles

We have theoretically studied the uptake of a non-uniformly charged biomolecule, suitable to represent a globular protein or a drug, by a charged hydrogel carrier in the presence of a 1:1 electrolyte. Based on the analysis of a physical interaction Hamiltonian including monopolar, dipolar and Born (self-energy) contributions derived from linear electrostatic theory of the unperturbed homogeneous hydrogel, we have identified five different sorption states of the system, from complete repulsion of the molecule to its full sorption deep inside the hydrogel, passing through meta- and stable surface adsorption states. The results are summarized in state diagrams that also explore the effects of varying the electrolyte concentration, the sign of the net electric charge of the biomolecule, and the role of including excluded-volume (steric) or hydrophobic biomolecule-hydrogel interactions. We show that the dipole moment of the biomolecule is a key parameter controlling the spatial distribution of the globules. In particular, biomolecules with a large dipole moment tend to be adsorbed at the external surface of the hydrogel, even if like-charged, whereas uniformly charged biomolecules tend to partition towards the internal core of an oppositely-charged hydrogel. Hydrophobic attraction shifts the states towards internal sorption of the biomolecule, whereas steric repulsion promotes surface adsorption for oppositely-charged biomolecules, or the total exclusion for likely-charged ones. Our results establish a guidance for the spatial partitioning of proteins and drugs in hydrogel carriers, tuneable by hydrogel charge, pH and salt concentration.Comment: 16 pages, 5 figure

Theoretical and Experimental Adsorption Studies of Polyelectrolytes on an Oppositely Charged Surface

Using self-assembly techniques, x-ray reflectivity measurements, and computer simulations, we study the effective interaction between charged polymer rods and surfaces. Long-time Brownian dynamics simulations are used to measure the effective adhesion force acting on the rods in a model consisting of a planar array of uniformly positively charged, stiff rods and a negatively charged planar substrate in the presence of explicit monovalent counterions and added monovalent salt ions in a continuous, isotropic dielectric medium. This electrostatic model predicts an attractive polymer-surface adhesion force that is weakly dependent on the bulk salt concentration and that shows fair agreement with a Debye-Huckel approximation for the macroion interaction at salt concentrations near 0.1 M. Complementary x-ray reflectivity experiments on poly(diallyldimethyl ammonium) chloride (PDDA) monolayer films on the native oxide of silicon show that monolayer structure, electron density, and surface roughness are likewise independent of the bulk ionic strength of the solution.Comment: Revtex, prb format; uses amssym

On Accelerated Inertial Frames in Gravity and Electromagnetism

When a charged insulating spherical shell is uniformly accelerated, an oppositely directed electric field is produced inside. Outside the field is the Born field of a uniformly accelerated charge, modified by a dipole. Radiation is produced. When the acceleration is annulled by the nearly uniform gravity field of an external shell with a 1 + beta cos theta surface distribution of mass, the differently viewed Born field is static and joins a static field outside the external shell; no radiation is produced. We discuss gravitational analogues of these phenomena. When a massive spherical shell is accelerated, an untouched test mass inside experiences a uniform gravity field and accelerates parallelly to the surrounding shell. In the strong gravity regime we illustrate these effects using exact conformastatic solutions of the Einstein-Maxwell equations with charged dust. We consider a massive charged shell on which the forces due to nearly uniform electrical and gravitational fields balance. Both fields are reduced inside by the ratio of the g_00 inside the shell to that away from it. The acceleration of a free test particle, relative to a static observer, is reduced correspondingly. We give physical explanations of these effects.Comment: 25 pages, LaTeX with 6 encapsulated postscript figures included. To appear in Annals of Physic