319 research outputs found
Competition of hydrophobic and Coulombic interactions between nano-sized solutes
The solvation of charged, nanometer-sized spherical solutes in water, and the
effective, solvent-induced force between two such solutes are investigated by
constant temperature and pressure Molecular Dynamics simulations of model
solutes carrying various charge patterns. The results for neutral solutes agree
well with earlier findings, and with predictions of simple macroscopic
considerations: substantial hydrophobic attraction may be traced back to strong
depletion (``drying'') of the solvent between the solutes. This hydrophobic
attraction is strongly reduced when the solutes are uniformly charged, and the
total force becomes repulsive at sufficiently high charge; there is a
significant asymmetry between anionic and cationic solute pairs, the latter
experiencing a lesser hydrophobic attraction. The situation becomes more
complex when the solutes carry discrete (rather than uniform) charge patterns.
Due to antagonistic effects of the resulting hydrophilic and hydrophobic
``patches'' on the solvent molecules, water is once more significantly depleted
around the solutes, and the effective interaction reverts to being mainly
attractive, despite the direct electrostatic repulsion between solutes.
Examination of a highly coarse-grained configurational probability density
shows that the relative orientation of the two solutes is very different in
explicit solvent, compared to the prediction of the crude implicit solvent
representation. The present study strongly suggests that a realistic modeling
of the charge distribution on the surface of globular proteins, as well as the
molecular treatment of water are essential prerequisites for any reliable study
of protein aggregation.Comment: 20 pages, 25 figure
Reduction of the hydrophobic attraction between charged solutes in water
We examine the effective force between two nanometer scale solutes in water
by Molecular Dynamics simulations. Macroscopic considerations predict a strong
reduction of the hydrophobic attraction between solutes when the latter are
charged. This is confirmed by the simulations which point to a surprising
constancy of the effective force between oppositely charged solutes at contact,
while like charged solutes lead to significantly different behavior between
positive and negative pairs. The latter exhibit the phenomenon of ``like-charge
attraction" previously observed in some colloidal dispersions.Comment: 4 pages, 5 figure
Communication: Resonance reaction in diffusion-influenced bimolecular reactions
We investigate the influence of a stochastically fluctuating step-barrier potential on bimolecular reaction rates by exact analytical theory and stochastic simulations. We demonstrate that the system exhibits a new "resonant reaction" behavior with rate enhancement if an appropriately defined fluctuation decay length is of the order of the system size. Importantly, we find that in the proximity of resonance, the standard reciprocal additivity law for diffusion and surface reaction rates is violated due to the dynamical coupling of multiple kinetic processes. Together, these findings may have important repercussions on the correct interpretation of various kinetic reaction problems in complex systems, as, e.g., in biomolecular association or catalysis
Polyelectrolyte-colloid complexes: polarizability and effective interaction
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 Waal's-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.Comment: 13 pages, 14 figure
A density--functional study of interfacial properties of colloid--polymer mixtures
Interfacial properties of colloid--polymer mixtures are examined within an
effective one--component representation, where the polymer degrees of freedom
are traced out, leaving a fluid of colloidal particles interacting via
polymer--induced depletion forces. Restriction is made to zero, one and
two--body effective potentials, and a free energy functional is used which
treats colloid excluded volume correlations within Rosenfeld's Fundamental
Measure Theory, and depletion--induced attraction within first--order
perturbation theory. This functional allows a consistent treatment of both
ideal and interacting polymers. The theory is applied to surface properties
near a hard wall, to the depletion interaction between two walls, and to the
fluid--fluid interface of demixed colloid--polymer mixtures. The results of the
present theory compare well with predictions of a fully two--component
representation of mixtures of colloids and ideal polymers (the Asakura--Oosawa
model), and allow a systematic investigation of the effects of polymer--polymer
interactions on interfacial properties. In particular, the wall surface tension
is found to be significantly larger for interacting than for ideal polymers,
while the opposite trend is predicted for the fluid--fluid interfacial tension.Comment: submitted to J. Phys. Chem. B, special issue in honour of David
Chandle
Coupling hydrophobic, dispersion, and electrostatic contributions in continuum solvent models
Recent studies of the hydration of micro- and nanoscale solutes have
demonstrated a strong {\it coupling} between hydrophobic, dispersion and
electrostatic contributions, a fact not accounted for in current implicit
solvent models. We present a theoretical formalism which accounts for coupling
by minimizing the Gibbs free energy with respect to a solvent volume exclusion
function. The solvent accessible surface is output of our theory. Our method is
illustrated with the hydration of alkane-assembled solutes on different length
scales, and captures the strong sensitivity to the particular form of the
solute-solvent interactions in agreement with recent computer simulations.Comment: 11 pages, 2 figure
Dynamical density functional theory: phase separation in a cavity and the influence of symmetry
Consider a fluid composed of two species of particles, where the
interparticle pair potentials . On confining an
equal number of particles from each species in a cavity, one finds that the
average one body density profiles of each species are constrained to be exactly
the same due to the symmetry, when both external cavity potentials are the
same. For a binary fluid of Brownian particles interacting via repulsive
Gaussian pair potentials that exhibits phase separation, we study the dynamics
of the fluid one body density profiles on breaking the symmetry of the external
potentials, using the dynamical density functional theory of Marconi and
Tarazona [{\it J. Chem. Phys.}, {\bf 110}, 8032 (1999)]. On breaking the
symmetry we see that the fluid one body density profiles can then show the
phase separation that is present.Comment: 7 pages, 4 figures. Accepted for the proceedings of the Liquid Matter
conference 2005, to be publication in J. Phys.: Condens. Matte
The van Hove distribution function for Brownian hard spheres: dynamical test particle theory and computer simulations for bulk dynamics
We describe a test particle approach based on dynamical density functional
theory (DDFT) for studying the correlated time evolution of the particles that
constitute a fluid. Our theory provides a means of calculating the van Hove
distribution function by treating its self and distinct parts as the two
components of a binary fluid mixture, with the `self' component having only one
particle, the `distinct' component consisting of all the other particles, and
using DDFT to calculate the time evolution of the density profiles for the two
components. We apply this approach to a bulk fluid of Brownian hard spheres and
compare to results for the van Hove function and the intermediate scattering
function from Brownian dynamics computer simulations. We find good agreement at
low and intermediate densities using the very simple Ramakrishnan-Yussouff
[Phys. Rev. B 19, 2775 (1979)] approximation for the excess free energy
functional. Since the DDFT is based on the equilibrium Helmholtz free energy
functional, we can probe a free energy landscape that underlies the dynamics.
Within the mean-field approximation we find that as the particle density
increases, this landscape develops a minimum, while an exact treatment of a
model confined situation shows that for an ergodic fluid this landscape should
be monotonic. We discuss possible implications for slow, glassy and arrested
dynamics at high densities.Comment: Submitted to Journal of Chemical Physic
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