16,158 research outputs found

### Interaction between like-charged polyelectrolyte-colloid complexes in electrolyte solutions: a Monte Carlo simulation study in the Debye-H\"uckel approximation

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 figure

### Fluid-fluid demixing transitions in colloid--polyelectrolyte star mixtures

We derive effective interaction potentials between hard, spherical colloidal
particles and star-branched polyelectrolytes of various functionalities and
smaller size than the colloids. The effective interactions are based on a
Derjaguin-like approximation, which is based on previously derived potentials
acting between polyelectrolyte stars and planar walls. On the basis of these
interactions we subsequently calculate the demixing binodals of the binary
colloid--polyelectrolyte star mixture, employing standard tools from
liquid-state theory. We find that the mixture is indeed unstable at moderately
high overall concentrations. The system becomes more unstable with respect to
demixing as the star functionality and the size ratio grow.Comment: 24 pages, 9 figures, submitted to Journal of Physics: Condensed
Matte

### Elasticity in strongly interacting soft solids: polyelectrolyte network

This paper discusses the elastic behavior of a very long crosslinked
polyelectrolyte chain (Debye-H\"uckel chain), which is weakly charged.
Therefore the response of the crosslinked chain (network) on an external
constant force $f$ acting on the ends of the chain is considered. A
selfconsistent variational computation of an effective field theory is
employed. It is shown, that the modulus of the polyelectrolyte network has two
parts: the first term represents the usual entropy elasticity of connected
flexible chains and the second term takes into account the electrostatic
interaction of the monomers. It is proportional to the squared crosslink
density and the Debye - screening parameter.Comment: submitted for publication to PR

### Molecular Dynamics Simulation of Semiflexible Polyampholyte Brushes - The Effect of Charged Monomers Sequence

Planar brushes formed by end-grafted semiflexible polyampholyte chains, each
chain containing equal number of positively and negatively charged monomers is
studied using molecular dynamics simulations. Keeping the length of the chains
fixed, dependence of the average brush thickness and equilibrium statistics of
the brush conformations on the grafting density and the salt concentration are
obtained with various sequences of charged monomers. When similarly charged
monomers of the chains are arranged in longer blocks, the average brush
thickness is smaller and dependence of brush properties on the grafting density
and the salt concentration is stronger. With such long blocks of similarly
charged monomers, the anchored chains bond to each other in the vicinity of the
grafting surface at low grafting densities and buckle toward the grafting
surface at high grafting densities.Comment: 8 pages,7 figure

### Conformational Instability of Rodlike Polyelectrolytes due to Counterion Fluctuations

The effective elasticity of highly charged stiff polyelectrolytes is studied
in the presence of counterions, with and without added salt. The rigid polymer
conformations may become unstable due to an effective attraction induced by
counterion density fluctuations. Instabilities at the longest, or intermediate
length scales may signal collapse to globule, or necklace states, respectively.
In the presence of added-salt, a generalized electrostatic persistence length
is obtained, which has a nontrivial dependence on the Debye screening length.
It is also found that the onset of conformational instability is a re-entrant
phenomenon as a function of polyelectrolyte length for the unscreened case, and
the Debye length or salt concentration for the screened case. This may be
relevant in understanding the experimentally observed re-entrant condensation
of DNA.Comment: 8 pages, 4 figure

### Effective Electrostatic Interactions in Suspensions of Polyelectrolyte Brush-Coated Colloids

Effective electrostatic interactions between colloidal particles, coated with
polyelectrolyte brushes and suspended in an electrolyte solvent, are described
via linear response theory. The inner cores of the macroions are modeled as
hard spheres, the outer brushes as spherical shells of continuously distributed
charge, the microions (counterions and salt ions) as point charges, and the
solvent as a dielectric continuum. The multi-component mixture of macroions and
microions is formally mapped onto an equivalent one-component suspension by
integrating out from the partition function the microion degrees of freedom.
Applying second-order perturbation theory and a random phase approximation,
analytical expressions are derived for the effective pair interaction and a
one-body volume energy, which is a natural by-product of the one-component
reduction. The combination of an inner core and an outer shell, respectively
impenetrable and penetrable to microions, allows the interactions between
macroions to be tuned by varying the core diameter and brush thickness. In the
limiting cases of vanishing core diameter and vanishing shell thickness, the
interactions reduce to those derived previously for star polyelectrolytes and
charged colloids, respectively.Comment: 20 pages, 5 figures, Phys. Rev. E (in press

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