Search

We study the effective interaction between differently charged polyelectrolyte-colloid complexes in electrolyte solutions via Monte Carlo simulations. These complexes are formed when short and flexible polyelectrolyte chains adsorb onto oppositely charged colloidal spheres, dispersed in an electrolyte solution. In our simulations the bending energy between adjacent monomers is small compared to the electrostatic energy, and the chains, once adsorbed, do not exchange with the solution, although they rearrange on the particles surface to accomodate further adsorbing chains or due to the electrostatic interaction with neighbor complexes. Rather unexpectedly, when two interacting particles approach each others, the rearrangement of the surface charge distribution invariably produces anti-parallel dipolar doublets, that invert their orientation at the isoelectric point. These findings clearly rule out a contribution of dipole-dipole interactions to the observed attractive interaction between the complexes, pointing out that such suspensions can not be considered dipolar fluids. On varying the ionic strength of the electrolyte, we find that a screening length, short compared with the size of the colloidal particles, is required in order to observe the attraction between like charged complexes due to the non-uniform distribution of the electric charge on their surface ('patch attraction'). On the other hand, by changing the polyelectrolyte/particle charge ratio, the interaction between like-charged polyelectrolyte-decorated (pd) particles, at short separations, evolves from purely repulsive to strongly attractive. Hence, the effective interaction between the complexes is characterized by a potential barrier, whose height depends on the net charge and on the non-uniformity of their surface charge distribution., Comment: 24 pages, 9 figures

In systems of highly charged linear polyelectrolytes and oppositely charged colloidal particles, long-lived clusters of polyelectrolyte-decorated particles form in an interval of concentrations around the isoelectric point, where reentrant condensation connected to charge inversion of cluster is observed. The mechanisms that drive the aggregation and stabilize, at the different polymer/particle ratios, a well defined size of the aggregates are not completely understood. Moreover, a central question still remains unanswered, i.e., whether the clusters are true equilibrium or metastable aggregates. To elucidate this point, in this work, we have investigated the effect of the temperature on the formation of the clusters. We employed liposomes built up by DOTAP lipid interacting with a simple anionic polyion, sodium polyacrylate, over an extended concentration range below and over the isoelectric condition. Our results show that the aggregation process can be described by a thermally-activated mechanism., Comment: Submitted Langmuir

The low-frequency limit of the electrical conductivity (d.c. conductivity) of differently flexible polyions in aqueous solutions has been measured over an extended polyion concentration range, covering both the dilute and semidilute (entangled and unentangled) regime, up to the concentrated regime. The data have been analyzed taking into account the different flexibility of the polymer chains according to the scaling theory of polyion solutions, in the case of flexible polyions, and according to the Manning model, in the case of rigid polyions. In both cases, the fraction f of free counterions, released into the aqueous phase from the ionizable polyion groups, has been evaluated and its dependence on the polyion concentration determined. Our results show that the counterion condensation follows at least three different regimes in dependence on the polyion concentration. The fraction f of free counterions remains constant only in the semidilute regime (a region that we have named the Manning regime), while there is a marked dependence on the polyion concentration both in the dilute and in the concentrated regime. These results are briefly discussed at the light of the aqueous ionic solutions., Comment: 9 pages, 8 figures

Polymer chains adsorbed onto oppositely charged spherical colloidal particles can significantly modify the particle-particle interactions. For sufficient amounts of added polymers, the original electrostatic repulsion can even turn into an effective attraction and relatively large kinetically stable aggregates can form which display several unexpected and interesting peculiarities and some intriguing biotechnological implications. The attractive interaction contribution between two oppositely particles arises from the correlated adsorption of polyions at the oppositely charged particle surfaces, resulting in a non-homogeneous surface charge distribution. Here, we investigate the aggregation kinetics of polyion-induced colloidal complexes through Monte Carlo simulation, in which the effect of charge anisotropy is taken into account by a DLVO-like intra-particle potential, as recentely proposed by Velegol and Thwar [D. Velegol and P.K. Thwar, Langmuir, 17, 2001]. The results reveal that in the presence of a charge heterogeneity the aggregation process slows down due to the progressive increase of the potential barrier height upon clustering. Within this framework, the experimentally observed cluster phases in polyelectrolyte-liposomes solutions should be considered as a kinetic arrested state., Comment: 9 pages. 11 figures