Polyelectrolyte-colloid complexes: polarizability and effective interaction

We theoretically study the polarizability and the interactions of neutral complexes consisting of a semi-flexible polyelectrolyte adsorbed onto an oppositely charged spherical colloid. In the systems we studied, the bending energy of the chain is small compared to the Coulomb energy and the chains are always adsorbed on the colloid. We observe that the polarizability is large for short chains and small electrical fields and shows a non-monotonic behavior with the chain length at fixed charge density. The polarizability has a maximum for a chain length equal to half of the circumference of the colloid. For long chains we recover the polarizability of a classical conducting sphere. For short chains, the existence of a permanent dipole moment of the complexes leads to a van der Waal's-type long-range attraction between them. This attractive interaction vanishes for long chains (i.e., larger than the colloidal size), where the permanent dipole moment is negligible. For short distances the complexes interact with a deep short-ranged attraction which is due to energetic bridging for short chains and entropic bridging for long chains. Exceeding a critical chain length eventually leads to a pure repulsion. This shows that the stabilization of colloidal suspensions by polyelectrolyte adsorption is strongly dependent on the chain size relative to the colloidal size: for long chains the suspensions are always stable (only repulsive forces between the particles), while for mid-sized and short chains there is attraction between the complexes and a salting-out can occur.Comment: 13 pages, 14 figure

Counterion density profiles at charged flexible membranes

Counterion distributions at charged soft membranes are studied using perturbative analytical and simulation methods in both weak coupling (mean-field or Poisson-Boltzmann) and strong coupling limits. The softer the membrane, the more smeared out the counterion density profile becomes and counterions pentrate through the mean-membrane surface location, in agreement with anomalous scattering results. Membrane-charge repulsion leads to a short-scale roughening of the membrane.Comment: 4 pages, 4 figure

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-Fluctuation-Induced Non-analytic Bending Rigidity

In this Letter, we consider a neutral system of mobile positive and negative charges confined on the surface of curved films. This may be an appropriate model for: i) a highly charged membrane whose counterions are confined to a sheath near its surface; ii) a membrane composed of an equimolar mixture of anionic and cationic surfactants in aqueous solution. We find that the charge fluctuations contribute a non-analytic term to the bending rigidity that varies logarithmically with the radius of curvature. This may lead to spontaneous vesicle formation, which is indeed observed in similar systems.Comment: Revtex, 9 pages, no figures, submitted to PR

Exact Lyapunov Exponent for Infinite Products of Random Matrices

In this work, we give a rigorous explicit formula for the Lyapunov exponent for some binary infinite products of random $2\times 2$ real matrices. All these products are constructed using only two types of matrices, $A$ and $B$, which are chosen according to a stochastic process. The matrix $A$ is singular, namely its determinant is zero. This formula is derived by using a particular decomposition for the matrix $B$, which allows us to write the Lyapunov exponent as a sum of convergent series. Finally, we show with an example that the Lyapunov exponent is a discontinuous function of the given parameter.Comment: 1 pages, CPT-93/P.2974,late

Role of Multipoles in Counterion-Mediated Interactions between Charged Surfaces: Strong and Weak Coupling

We present general arguments for the importance, or lack thereof, of the structure in the charge distribution of counterions for counterion-mediated interactions between bounding symmetrically charged surfaces. We show that on the mean field or weak coupling level, the charge quadrupole contributes the lowest order modification to the contact value theorem and thus to the intersurface electrostatic interactions. The image effects are non-existent on the mean-field level even with multipoles. On the strong coupling level the quadrupoles and higher order multipoles contribute additional terms to the interaction free energy only in the presence of dielectric inhomogeneities. Without them, the monopole is the only multipole that contributes to the strong coupling electrostatics. We explore the consequences of these statements in all their generality.Comment: 12 pages, 3 figure

On the signature of tensile blobs in the scattering function of a stretched polymer

We present Monte Carlo data for a linear chain with excluded volume subjected to a uniform stretching. Simulation of long chains (up to 6000 beads) at high stretching allows us to observe the signature of tensile blobs as a crossover in the scaling behavior of the chain scattering function for wave vectors perpendicular to stretching. These results and corresponding ones in the stretching direction allow us to verify for the first time Pincus prediction on scaling inside blobs. Outside blobs, the scattering function is well described by the Debye function for a stretched ideal chain.Comment: 4 pages, 4 figures, to appear in Physical Review Letter

Electrolytic depletion interactions

We consider the interactions between two uncharged planar macroscopic surfaces immersed in an electrolyte solution which are induced by interfacial selectivity. These forces are taken into account by introducing a depletion free-energy density functional, in addition to the usual mean-field Poisson-Boltzmann functional. The minimization of the total free-energy functional yields the density profiles of the microions and the electrostatic potential. The disjoining pressure is obtained by differentiation of the total free energy with respect to the separation of the surfaces, holding the range and strength of the depletion forces constant. We find that the induced interaction between the two surfaces is always repulsive for sufficiently large separations, and becomes attractive at shorter separations. The nature of the induced interactions changes from attractive to repulsive at a distance corresponding to the range of the depletion forces.Comment: 17 pages, 4 Postscript figures, submitted to Physical Review

MDHAQ/RAPID3 scores in patients with osteoarthritis are similar to or higher than in patients with rheumatoid arthritis: A cross-sectional study from current routine rheumatology care at four sites

Objective To compare patients with a primary diagnosis of osteoarthritis (OA) versus rheumatoid arthritis (RA) for scores on a patient self-report MDHAQ/RAPID3 (Multidimensional Health Assessment Questionnaire/Routine Assessment of Patient Index Data 3), and for physician global assessment (DOCGL). Methods All patients with all diagnoses complete an MDHAQ/RAPID3 at all routine rheumatology visits in the waiting area before seeing a rheumatologist at four sites, one in Australia and three in the USA. The two-page MDHAQ includes 0-10 scores for physical function (in 10 activities), pain and patient global assessment [on 0-10 visual analogue scales (VAS)], compiled into a 0-30 RAPID3, as well as fatigue and self-report painful joint count scales. Rheumatologists estimate a 0-10 DOCGL VAS. Demographic, MDHAQ/RAPID3 and DOCGL data from a random visit were compared in patients with RA versus patients with OA using multivariate analysis of variance, adjusted for age, disease duration and formal education level. Results Median RAPID3 was higher in OA versus RA at all four sites (11.7-16.8 vs 6.2-11.8) (p<0.001 at three sites). Median DOCGL in OA versus RA was 5 vs 4, 4 vs 3.7, 2.2 vs 2.5 and 2 vs 1. Patterns were similar for individual RAPID3 items, fatigue and painful joint scales, and in stratified analyses of patients aged 55-70. Conclusion Patient MDHAQ/RAPID3 and physician DOCGL indicate similar or higher disease burden in OA versus RA. Routine MDHAQ/RAPID3 allows direct comparisons of the two diseases. The findings suggest possible revision of current clinical and public policy views concerning OA