119 research outputs found
Charge-Reversal Instability in Mixed Bilayer Vesicles
Bilayer vesicles form readily from mixtures of charged and neutral
surfactants. When such a mixed vesicle binds an oppositely-charged object, its
membrane partially demixes: the adhesion zone recruits more charged surfactants
from the rest of the membrane. Given an unlimited supply of adhering objects
one might expect the vesicle to remain attractive until it was completely
covered. Contrary to this expectation, we show that a vesicle can instead
exhibit {\it adhesion saturation,} partitioning spontaneously into an
attractive zone with definite area fraction, and a repulsive zone. The latter
zone rejects additional incoming objects because counterions on the interior of
the vesicle migrate there, effectively reversing the membrane's charge. The
effect is strongest at high surface charge densities, low ionic strength, and
with thin, impermeable membranes. Adhesion saturation in such a situation has
recently been observed experimentally [H. Aranda-Espinoza {\it et al.}, {\sl
Science} {\bf285} 394--397 (1999)]
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
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
The osmotic pressure of charged colloidal suspensions: A unified approach to linearized Poisson-Boltzmann theory
We study theoretically the osmotic pressure of a suspension of charged
objects (e.g., colloids, polyelectrolytes, clay platelets, etc.) dialyzed
against an electrolyte solution using the cell model and linear
Poisson-Boltzmann (PB) theory. From the volume derivative of the grand
potential functional of linear theory we obtain two novel expressions for the
osmotic pressure in terms of the potential- or ion-profiles, neither of which
coincides with the expression known from nonlinear PB theory, namely, the
density of microions at the cell boundary. We show that the range of validity
of linearization depends strongly on the linearization point and proof that
expansion about the selfconsistently determined average potential is optimal in
several respects. For instance, screening inside the suspension is
automatically described by the actual ionic strength, resulting in the correct
asymptotics at high colloid concentration. Together with the analytical
solution of the linear PB equation for cell models of arbitrary dimension and
electrolyte composition explicit and very general formulas for the osmotic
pressure ensue. A comparison with nonlinear PB theory is provided. Our analysis
also shows that whether or not linear theory predicts a phase separation
depends crucially on the precise definition of the pressure, showing that an
improper choice could predict an artificial phase separation in systems as
important as DNA in physiological salt solution.Comment: 16 pages, 5 figures, REVTeX4 styl
Charge Fluctuations and Counterion Condensation
We predict a condensation phenomenon in an overall neutral system, consisting
of a single charged plate and its oppositely charged counterions. Based on the
``two-fluid'' model, in which the counterions are divided into a ``free'' and a
``condensed'' fraction, we argue that for high surface charge, fluctuations can
lead to a phase transition in which a large fraction of counterions is
condensed. Furthermore, we show that depending on the valence, the condensation
is either a first-order or a smooth transition.Comment: 16 pages, 1 figure, accepted to be published in PR
Counterion Condensation and Fluctuation-Induced Attraction
We consider an overall neutral system consisting of two similarly charged
plates and their oppositely charged counterions and analyze the electrostatic
interaction between the two surfaces beyond the mean-field Poisson-Boltzmann
approximation. Our physical picture is based on the fluctuation-driven
counterion condensation model, in which a fraction of the counterions is
allowed to ``condense'' onto the charged plates. In addition, an expression for
the pressure is derived, which includes fluctuation contributions of the whole
system. We find that for sufficiently high surface charges, the distance at
which the attraction, arising from charge fluctuations, starts to dominate can
be large compared to the Gouy-Chapmann length. We also demonstrate that
depending on the valency, the system may exhibit a novel first-order binding
transition at short distances.Comment: 15 pages, 8 figures, to appear in PR
Attraction between DNA molecules mediated by multivalent ions
The effective force between two parallel DNA molecules is calculated as a
function of their mutual separation for different valencies of counter- and
salt ions and different salt concentrations. Computer simulations of the
primitive model are used and the shape of the DNA molecules is accurately
modelled using different geometrical shapes. We find that multivalent ions
induce a significant attraction between the DNA molecules whose strength can be
tuned by the averaged valency of the ions. The physical origin of the
attraction is traced back either to electrostatics or to entropic
contributions. For multivalent counter- and monovalent salt ions, we find a
salt-induced stabilization effect: the force is first attractive but gets
repulsive for increasing salt concentration. Furthermore, we show that the
multivalent-ion-induced attraction does not necessarily correlate with DNA
overcharging.Comment: 51 pages and 13 figure
Hydration interactions: aqueous solvent effects in electric double layers
A model for ionic solutions with an attractive short-range pair interaction
between the ions is presented. The short-range interaction is accounted for by
adding a quadratic non-local term to the Poisson-Boltzmann free energy. The
model is used to study solvent effects in a planar electric double layer. The
counter-ion density is found to increase near the charged surface, as compared
with the Poisson-Boltzmann theory, and to decrease at larger distances. The ion
density profile is studied analytically in the case where the ion distribution
near the plate is dominated only by counter-ions. Further away from the plate
the density distribution can be described using a Poisson-Boltzmann theory with
an effective surface charge that is smaller than the actual one.Comment: 11 Figures in 13 files + LaTex file. 20 pages. Accepted to Phys. Rev.
E. Corrected typos and reference
Effective interaction between helical bio-molecules
The effective interaction between two parallel strands of helical
bio-molecules, such as deoxyribose nucleic acids (DNA), is calculated using
computer simulations of the "primitive" model of electrolytes. In particular we
study a simple model for B-DNA incorporating explicitly its charge pattern as a
double-helix structure. The effective force and the effective torque exerted
onto the molecules depend on the central distance and on the relative
orientation. The contributions of nonlinear screening by monovalent counterions
to these forces and torques are analyzed and calculated for different salt
concentrations. As a result, we find that the sign of the force depends
sensitively on the relative orientation. For intermolecular distances smaller
than it can be both attractive and repulsive. Furthermore we report a
nonmonotonic behaviour of the effective force for increasing salt
concentration. Both features cannot be described within linear screening
theories. For large distances, on the other hand, the results agree with linear
screening theories provided the charge of the bio-molecules is suitably
renormalized.Comment: 18 pages, 18 figures included in text, 100 bibliog
Adsorption of mono- and multivalent cat- and anions on DNA molecules
Adsorption of monovalent and multivalent cat- and anions on a deoxyribose
nucleic acid (DNA) molecule from a salt solution is investigated by computer
simulation. The ions are modelled as charged hard spheres, the DNA molecule as
a point charge pattern following the double-helical phosphate strands. The
geometrical shape of the DNA molecules is modelled on different levels ranging
from a simple cylindrical shape to structured models which include the major
and minor grooves between the phosphate strands. The densities of the ions
adsorbed on the phosphate strands, in the major and in the minor grooves are
calculated. First, we find that the adsorption pattern on the DNA surface
depends strongly on its geometrical shape: counterions adsorb preferentially
along the phosphate strands for a cylindrical model shape, but in the minor
groove for a geometrically structured model. Second, we find that an addition
of monovalent salt ions results in an increase of the charge density in the
minor groove while the total charge density of ions adsorbed in the major
groove stays unchanged. The adsorbed ion densities are highly structured along
the minor groove while they are almost smeared along the major groove.
Furthermore, for a fixed amount of added salt, the major groove cationic charge
is independent on the counterion valency. For increasing salt concentration the
major groove is neutralized while the total charge adsorbed in the minor groove
is constant. DNA overcharging is detected for multivalent salt. Simulations for
a larger ion radii, which mimic the effect of the ion hydration, indicate an
increased adsorbtion of cations in the major groove.Comment: 34 pages with 14 figure
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