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.

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.

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.

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.

Dendron brushes and dendronized polymers: a theoretical outlook.

Dendron brushes are molecular structures built up of treelike macromolecules, with multiple generations of branches, grafted with a root segment to a surface (particle) or to a backbone chain (dendronized polymer) with a sufficiently high grafting density so that the dendrons interact laterally. Recent advances in the theory of dendron brushes are highlighted and complemented by insights from numerical self-consistent field modelling. Our focus is on controversial issues, which are still under debate, such as, the strain distribution in individual dendrons and the appearance of distinct populations with a different extent of stretching for dendrons in planar brushes.