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 $R^{-5}$ or $R^{-4}$; monopolar energies vary as $R^{-1}$ or $\ln{R}$, where $R$ 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