3 research outputs found
Modeling of Ionization and Conformations of Starlike Weak Polyelectrolytes
The
target of this work is to study conformational properties of
starlike polyelectrolytes with pH-sensitive (annealed) dissociation
in salt-free solutions. We confront hybrid Monte Carlo (HMC) simulations
with computationally less expensive approximate numerical self-consistent
field (SCF) calculations and with analytical theories. We demonstrate
when the mean-field results are reliable and their advantage over
MC in terms of efficiency can be exploited and when not. In the interior
of the star, where inter-arm interactions dominate over intra-arm
ones, the mean-field approximation works well and SCF agrees with
the MC results. Intra-arm interactions dominate at star periphery,
and their role is underestimated by the mean field. Here, conformations
and dissociation resemble those of linear polyelectrolytes. Consequently,
the dissociation profile along the chain contour is qualitatively
different between MC and SCF. Comparison of the two methods and a
distinction between intra-arm and inter-arm contributions to interactions
enables us to understand the transition in behavior from linear to
starlike chain topology
Impact of Macromolecular Architecture on Bending Rigidity of Dendronized Surfaces
Nanomechanical
properties of natural and artificial nanomembranes
can be strongly affected by anchored or tethered macromolecules. The
intermolecular interactions in polymeric layers give rise to so-called
induced bending rigidity which complements the bare rigidity of the
membrane. Using analytical mean-field theory, we explore how macromolecular
architecture of tethered polymers affects the bending rigidities of
the polymer-decorated membranes. The developed theory enables us to
consider explicitly various polymer architectures including regular
dendrons, Ψ-shaped, star- and comblike macromolecules as well
as macrocycles. Numerical self-consistent field computations for selected
(regular dendritic) topology complement the analytical theory and
support its predictions. We consider both cases of (i) quenched symmetric
distribution of tethered molecules on both sides of the membrane and
(ii) annealing distribution in which the tethered polymers can relocate
from the concave to the convex side of the membrane upon bending.
We demonstrate that at a given surface coverage an increase in the
degree of branching or cyclization leads to the decrease in the induced
bending rigidity. Relocation of the tethered molecules from concave
to convex surfaces leads to the additional decrease in polymer contribution
to the membrane bending rigidity. In the latter case, a decrease in
configurational entropy due to this redistributions substantially
contributes to the bending rigidity
Impact of Macromolecular Architecture on Bending Rigidity of Dendronized Surfaces
Nanomechanical
properties of natural and artificial nanomembranes
can be strongly affected by anchored or tethered macromolecules. The
intermolecular interactions in polymeric layers give rise to so-called
induced bending rigidity which complements the bare rigidity of the
membrane. Using analytical mean-field theory, we explore how macromolecular
architecture of tethered polymers affects the bending rigidities of
the polymer-decorated membranes. The developed theory enables us to
consider explicitly various polymer architectures including regular
dendrons, Ψ-shaped, star- and comblike macromolecules as well
as macrocycles. Numerical self-consistent field computations for selected
(regular dendritic) topology complement the analytical theory and
support its predictions. We consider both cases of (i) quenched symmetric
distribution of tethered molecules on both sides of the membrane and
(ii) annealing distribution in which the tethered polymers can relocate
from the concave to the convex side of the membrane upon bending.
We demonstrate that at a given surface coverage an increase in the
degree of branching or cyclization leads to the decrease in the induced
bending rigidity. Relocation of the tethered molecules from concave
to convex surfaces leads to the additional decrease in polymer contribution
to the membrane bending rigidity. In the latter case, a decrease in
configurational entropy due to this redistributions substantially
contributes to the bending rigidity