The Structure of Dipolar Polymer Brushes and Their Interaction in the Melt. Impact of Chain Stiffness.

By using the numerical lattice Scheutjens-Fleer self-consistent field (SF-SCF) method we have studied the effect of the restricted flexibility of grafted chains on the structure and mutual interaction of two opposing planar conventional and A-type dipolar brushes. Brushes are immersed in the solvent consisting of chains similar to the grafted ones. The increase of the chain rigidity enhances the segregation of grafted chains in a A-type dipolar brush into two populations: backfolded chains with terminal monomers near the grafting surface and chains with the ends at the brush periphery. The fraction of backfolded chains grows by an increase of the Kuhn segment length. It is shown that two opposite A-type dipolar brushes from semi-rigid chains are attracted to each other at short distances. The attraction becomes more pronounced and begins at larger distances for more rigid chains with the same brush characteristics: polymerization degree, grafting density, and dipole moments of monomer units. This attraction is connected with the dipole-dipole interactions between chains of oncoming brushes with oppositely directed dipoles penetrating deeply into each other upon contact. This effect of the chain rigidity is opposite to that for conventional brushes without dipoles in the chains. For such brushes, an increase in the chain rigidity leads to the enhanced repulsion between them.

Cascades of unfolding transitions in amphiphilic molecular brushes.

Using a combination of self-consistent field theory with coarse-grained Brownian dynamics simulations, we studied mechanical unfolding of an amphiphilic molecular brush in a solvent that was poor for the side chains but good for the main chain of the brush. In striking contrast to earlier theoretical predictions [O. V. Borisov and A. Halperin, Europhys. Lett. 34, 657 (1996)] made for amphiphilic graft copolymers, we discovered that in a partially unfolded molecular brush, a globular core co-exists, at equilibrium, with a necklace of smaller sized intra-molecular micelles, each comprising a few side chains connected by stretched main chain strands (bridges). A progressive increase in the main chain end-to-end distance of the brush triggers a sequence of discrete events of generation of new intramolecular micelles, giving rise to a sawtooth pattern in the restoring force-deformation curve.

Unfolding of a comb-like polymer in a poor solvent: translation of macromolecular architecture in the force-deformation spectra.

A numerical self-consistent field modeling approach was employed to study the mechanical unfolding of a globule made by comb-like polymers in a poor solvent with the aim of unraveling how the macromolecular architecture affects the shape of the single-molecule force-deformation curves. We demonstrate that the dependence of the restoring force on the imposed extension of the main chain of the comb-like polymer exhibits a characteristic oscillatory shape in the intermediate deformation range. Theoretical arguments are developed that enable us to relate the shape of the patterns on the force-deformation curves to the molecular architecture (grafting density and length of the side chains) and interaction parameters. Thus, the results of our study suggest a new approach for the determination of macromolecular topology from single-molecule mechanical unfolding experiments.

Formation of a "Hollow" Interior in the Fourth-Generation Dendrimer with Attached Oligomeric Terminal Segments.

By using the Scheutjens-Fleer self-consistent field approach, the structure of the fourth-generation dendrimer with attached terminal chemically different oligomeric segments is studied theoretically. It is demonstrated that an incompatibility of terminal segments with inner dendrimer units leads to formation of a "hollow" core with reduced polymer density in the dendrimer center. This effect is enhanced with a deterioration in the solvent quality for terminal segments. This observation is in accordance with experimental results and molecular dynamics simulation data for an analogous system. It is established that the main factor determining the hollow core formation is the segregation between inner and terminal units because the main driving force for the effect is the localization of the terminal segments at the dendrimer periphery. The influence of structural parameters of dendrimer such as the number of generations and length of the terminal chain on this effect is also studied.

Interaction of a hydrophobic weak polyelectrolyte star with an apolar surface.

We consider star-like polymers with weak, that is, pH-dependent, hydrophobic polyelectrolyte arms. For low ionic strength conditions, a microphase-segregated quasimicellar structure is found, for which the star features a compact apolar core and a charged and swollen corona. This state is jump-like lost when the ionic strength is increased, i.e., at some intermediate ionic strength value. Using numerical self-consistent field modeling, we focus on the adsorption characteristics of these objects onto hydrophobic surfaces as a function of the ionic strength. In the quasimicellar state, the stars are attracted to the surface, albeit that, typically, an adsorption barrier is present. The strongest repulsion is found at intermediate ionic strength, where the star-like molecule is in a single-phase state and the barrier remains modest at both low and high ionic strength cases. Remarkably, it is possible that a star in a single swollen phase state is pushed into the quasimicellar state.