Impact of Macromolecular Architecture on Bending Rigidity of Dendronized Surfaces

Abstract

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.

Complexes of end-functionalized polystyrenes carrying amine end-group with transition metals: association effects in organic solvents

“…These studies include various fields of research, such as macrophase and microphase separation [3][4][5], gelation [6][7][8], crystallization [9,10] and association phenomena [11][12][13]. The progress in this area is closely related to the advances in the synthesis of well-defined macromolecular structures having the maximum control over the molecular characteristics and the architecture [14][15][16][17][18][19][20][21][22].…”

The effect of dendritic pendants on the folding of amphiphilic copolymers via supramolecular interactions

“…While some studies suggest that dendritic pendants, compared to linear pendants, induce stretching of a polymer chain at lower degrees of incorporation or via the use of smaller pendants, others suggest no influence of the degree of branching . Furthermore, surfaces, such as membranes, are expected to become less rigid, and thus more bendable, when grafted with more branched architectures …”

“…[45][46][47][48] Furthermore, surfaces, such as membranes, are expected to become less rigid, and thus more bendable, when grafted with more branched architectures. 49,50 Nowadays, a popular method to control the conformation of synthetic polymers is the so-called single-chain polymeric nanoparticles (SCPNs) approach. Here, individual polymers are intramolecularly collapsed into nanoparticles by means of covalent, dynamic covalent, or supramolecular crosslinks.…”