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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 Waals-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.
Complexation between anionic and cationic polyelectrolytes results in solid-like precipitates or liquid-like coacervate depending on the added salt in the aqueous medium. However, the boundary between these polymer-rich phases is quite broad and the
We study the adsorption of charged patchy particle models (CPPMs) on a thin film of a like-charged and dense polyelectrolyte (PE) brush (of 50 monomers per chain) by means of implicit-solvent, explicit-salt Langevin dynamics computer simulations. Our
Multilamellar wall vesicles (MLWV) are an interesting class of polyelectrolyte-surfactant complexes (PESCs) for wide applications ranging from house-care to biomedical products. If MLWV are generally obtained by a polyelectrolyte-driven vesicle agglu
We investigate a system of dense polyelectrolytes in solution. The Langevin dynamics of the system with linearized hydrodynamics is formulated in the functional integral formalism and a transformation made to collective coordinates. Within a dynamica
The structure of spherical micelles of the diblock copolymer poly(styrene-block-acrylic acid) in water was investigated with small angle neutron scattering (SANS) and contrast matching. We have monitored inter-micelle correlation and the extension of