55 research outputs found
Model charged cylindrical nanopore in a colloidal dispersion: charge reversal, overcharging and double overcharging
Using the hypernetted-chain/mean spherical approximation (HNC/MSA) integral
equations we study the electrical double layer inside and outside a model
charged cylindrical vesicle (nanopore) immersed into a primitive model
macroions solution, so that the macroions are only present outside the
nanopore, i.e., the vesicle wall is impermeable only to the external macroions.
We calculate the ionic and local linear charge density profiles inside and
outside the vesicle, and find that the correlation between the inside and
outside ionic distributions causes the phenomena of overcharging (also referred
to as surface charge amplification) and/or charge reversal. This is the first
time overcharging is predicted in an electrical double layer of cylindrical
geometry. We also report the new phenomenon of double overcharging. The present
results can be of consequence for relevant systems in physical-chemistry,
energy storage and biology, e.g., nanofilters, capacitors and cell membranes.Comment: 10 pages, 4 figure
Overcharging: The Crucial Role of Excluded Volume
In this Letter we investigate the mechanism for overcharging of a single
spherical colloid in the presence of aqueous salts within the framework of the
primitive model by molecular dynamics (MD) simulations as well as
integral-equation theory. We find that the occurrence and strength of
overcharging strongly depends on the salt-ion size, and the available volume in
the fluid. To understand the role of the excluded volume of the microions, we
first consider an uncharged system. For a fixed bulk concentration we find that
upon increasing the fluid particle size one strongly increases the local
concentration nearby the colloidal surface and that the particles become
laterally ordered. For a charged system the first surface layer is built up
predominantly by strongly correlated counterions. We argue that this a key
mechanism to produce overcharging with a low electrostatic coupling, and as a
more practical consequence, to account for charge inversion with monovalent
aqueous salt ions.Comment: 7 pages, 3 figs (4 EPS files). To appear in Europhysics Letter
Entropy driven key-lock assembly
The effective interaction between a sphere with an open cavity (lock) and a
spherical macroparticle (key), both immersed in a hard sphere fluid, is studied
by means of Monte Carlo simulations. As a result, a 2d map of the key-lock
effective interaction potential is constructed, which leads to the proposal of
a self-assembling mechanism: there exists trajectories through which the
key-lock pair could assemble avoiding trespassing potential barriers. Hence,
solely the entropic contribution can induce their self-assembling even in the
absence of attractive forces. This study points out the solvent contribution
within the underlying mechanisms of substrate-protein assembly/disassembly
processes, which are important steps of the enzyme catalysis and protein
mediated transport
The electrical double layer for a fully asymmetric electrolyte around a spherical colloid: an integral equation study
The hypernetted chain/mean spherical approximation (HNC/MSA) integral
equation is obtained and solved numerically for a totally asymmetric primitive
model electrolyte around a spherical macroparticle. The ensuing radial
distribution functions show a very good agreement when compared to our Monte
Carlo and molecular dynamics simulations for spherical geometry and with
respect to previous anisotropic reference HNC calculations in the planar limit.
We report an analysis of the potential vs charge relationship, radial
distribution functions, mean electrostatic potential and cumulative reduced
charge for representative cases of 1:1 and 2:2 salts with a size asymmetry
ratio of 2. Our results are collated with those of the Modified Gouy-Chapman
(MGC) and unequal radius Modified Gouy-Chapman (URMGC) theories and with those
of HNC/MSA in the restricted primitive model (RPM) to assess the importance of
size asymmetry effects. One of the most striking characteristics found is
that,\textit{contrary to the general belief}, away from the point of zero
charge the properties of an asymmetric electrical double layer (EDL) are not
those corresponding to a symmetric electrolyte with the size and charge of the
counterion, i.e. \textit{counterions do not always dominate}. This behavior
suggests the existence of a new phenomenology in the EDL that genuinely belongs
to a more realistic size-asymmetric model where steric correlations are taken
into account consistently. Such novel features can not be described by
traditional mean field theories like MGC, URMGC or even by enhanced formalisms,
like HNC/MSA, if they are based on the RPM.Comment: 29 pages, 13 figure
Electrophoresis of a rod macroion under polyelectrolyte salt: Is mobility reversed for DNA?
By molecular dynamics simulation, we study the charge inversion phenomenon of
a rod macroion in the presence of polyelectrolyte counterions. We simulate
electrophoresis of the macroion under an applied electric field. When both
counterions and coions are polyelectrolytes, charge inversion occurs if the
line charge density of the counterions is larger than that of the coions. For
the macroion of surface charge density equal to that of the DNA, the reversed
mobility is realized either with adsorption of the multivalent counterion
polyelectrolyte or the combination of electrostatics and other mechanisms
including the short-range attraction potential or the mechanical twining of
polyelectrolyte around the rod axis.Comment: 8 pages, 5 figures, Applied Statistical Physics of Molecular
Engineering (Mexico, 2003). Journal of Physics: Condensed Matters, in press
(2004). Journal of Physics: Condensed Matters, in press (2004
DNA condensation and redissolution: Interaction between overcharged DNA molecules
The effective DNA-DNA interaction force is calculated by computer simulations
with explicit tetravalent counterions and monovalent salt. For overcharged DNA
molecules, the interaction force shows a double-minimum structure. The
positions and depths of these minima are regulated by the counterion density in
the bulk. Using two-dimensional lattice sum and free energy perturbation
theories, the coexisting phases for DNA bundles are calculated. A
DNA-condensation and redissolution transition and a stable mesocrystal with an
intermediate lattice constant for high counterion concentration are obtained.Comment: 26 pages, 10 figure
Charge Fluctuation Forces Between Stiff Polyelectrolytes in Salt Solution: Pairwise Summability Re-examined
We formulate low-frequency charge-fluctuation forces between charged
cylinders - parallel or skewed - in salt solution: forces from dipolar van der
Waals fluctuations and those from the correlated monopolar fluctuations of
mobile ions. At high salt concentrations forces are exponentially screened. In
low-salt solutions dipolar energies go as or ; monopolar
energies vary as or , where is the minimal separation
between cylinders. However, pairwise summability of rod-rod forces is easily
violated in low-salt conditions. Perhaps the most important result is not the
derivation of pair potentials but rather the demonstration that some of these
expressions may not be used for the very problems that originally motivated
their derivation.Comment: 8 pages and 1 fig in ps forma
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