0000000000273807
AUTHOR
O. V. Borisov
Polyelectrolyte Molecule in an Elongational Flow
The theory describing the stretching of a weakly charged polyelectrolyte molecule by elongational shear flow is developed. It is shown that for a polyelectrolyte immersed in a salt-added solution two critical values of shear flow gradient exist: the lower critical point corresponds to the chain stretching on the scale of superblobs of size equal to the Debye screening length and the upper critical point corresponds to the complete stretching of the chain on the scale of monomer units.
Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology
Block copolymers self-assemble into a variety of nanostructures that are relevant for science and technology. While the assembly of diblock copolymers is largely understood, predicting the solution assembly of triblock terpolymers remains challenging due to complex interplay of block/block and block/solvent interactions. Here we provide guidelines for the self-assembly of linear ABC triblock terpolymers into a large variety of multicompartment nanostructures with C corona and A/B cores. The ratio of block lengths NC/NA thereby controls micelle geometry to spheres, cylinders, bilayer sheets and vesicles. The insoluble blocks then microphase separate to core A and surface patch B, where NB co…
Micelles of Polysoaps: The Role of Bridging Interactions
Polysoaps, hydrophilic polymers incorporating amphiphilic monomers, form intrachain micelles in aqueous media. The micelles are similar to those formed by monomeric amphiphiles but are also endowed with a swollen, starlike corona formed by the spacer chains joining the amphiphiles. Long polysoaps form strings comprising many intrachain micelles. Exchange of amphiphiles between such micelles may give rise to bridging attraction, resulting in the adoption of a collapsed configuration in which the swollen micelles are close packed into a spherical globule. Upon addition of free amphiphiles, this structure unravels in a highly nonlinear fashion. Titration by surfactants, and the resulting swell…
Splitting of Surface-Immobilized Multicompartment Micelles into Clusters upon Charge Inversion
International audience; We investigate a morphological transition of surface-immobilized triblock terpolymer micelles: the splitting into well-defined clusters of satellite micelles upon pH changes. The multicompartment micelles are formed in aqueous solution of ABC triblock terpolymers consisting of a hydrophobic polybutadiene block, a weak polyanionic poly(methacrylic acid) block, and a weak polycationic poly(2-(dimethylamino)ethyl methacrylate) block. They are subsequently immobilized on silicon wafer surfaces by dip-coating. The splitting process is triggered by a pH change to strongly basic pH, which goes along with a charge reversal of the micelles. We find that the aggregation number…
Polyelectrolytes Grafted to Curved Surfaces
We present a scaling theory to describe equilibrium conformations of weakly charged polyelectrolyte molecules grafted at one end onto impermeable surfaces of various morphologies (spheres, cylinders) and of arbitrary curvature. We focus on the case of sufficiently densely grafted chains, i.e., on curved polyelectrolyte brushes. Different regimes of the behavior of curved polyelectrolyte brushes can be distinguished, depending on grafting density, surface curvature, and chain length. We present phase diagrams of the system describing these regimes and discuss the crossover conditions. We also analyze the effect of charge annealing in curved polyelectrolyte brushes.
Comb-Branched Polymers: Monte Carlo Simulation and Scaling
The Monte Carlo simulation technique (the bond fluctuation model) has been used for the study of the equilibrium conformations of comb-branched polymers consisting of a long flexible main chain and side chains grafted at a regular separation onto the main chain. The solvent has been supposed to be good (athermal) for the main and side chains. The global conformation and the gyration radius of the polymer, as well as the local conformational structure of the comb, have been analyzed as functions of the length of the side chains and spacers. The effect of induced rigidity of the comb due to the interaction between side chains has been observed. We have found the results of the simulation to b…
Conformations of Star-Branched Polyelectrolytes
Scaling theory describing the conformations of weakly charged star-branched polyelectrolytes in dilute and semi-dilute salt-free solutions is developed. The dependence of the star size on the number of branches as well as on the solution concentration is analyzed. It is shown that the star size increases with an increase in the number of branches, f, at small f and tends to a constant value at large f. An increase in the concentration of stars in a solution results in a decrease in the star size R according to the power low : R ∼ c -1/3 in the range of a moderate concentration and R ∼ c -1/4 at larger concentration. For stars with a small number of branches the behavior R ∼ c -1/2 in a cert…
Stochastic dynamics simulation of grafted polymer brushes under shear deformation
We present results of computer simulations of polymer brushes (layers of polymer chains attached at one end onto an impermeable planar surface) under shear deformation at constant shear rate. As the first stage of calculations the behavior of a single brush was studied. The monomer density profile, the distribution of the chain ends, the positions and orientations of different monomers along the chain were calculated. Dimensions of the polymer chains as functions of the shear rate were obtained for different grafting densities. An increase in the brush thickness over the grafting plane with an increase in the shear rate as predicted by the theory of Barrat was observed. However, the magnitu…