The Effects of Crowding in Dendronized Polymers

Abstract

We present a comprehensive numerical study of the effect of degree of polymerization, generation of dendron growth, length of dendron tether, and dendron grafting density on the conformational statistics of dendronized polymers. This class of supramolecular assembly promises to find application in a number of nanotechnological devices in which their dimensions and conformations are key. We find that the radius of gyration estimates obtained from Brownian dynamics simulations yield to a "Flory" scaling argument in the high degree of polymerization regime and that these data from a range of topologically distinct molecules collapse onto a single curve in this limit. The size of the tethered dendrons serve as the key parameter in the scaling theory. Close examination of the dendrons also reveals some curious trends. In particular, we observe that as the grafting density is increased, spatial packing constraints around the main chain backbone force the dendrons further away from the backbone and compress them, significantly affecting the spatial distribution and accessibility of terminal groups; in contrast to dendrimers, the terminal groups of these molecules display a tendency to partition near the surface at high dendron grafting densities.

Synthesis and characterization of linear dendritic homo and copolymers acrylated behera amine

“…[1][2][3][4] Within the studies in the literature, generally comparisons of theoretical and experimental results were made with respect to the topographies of dendritic structures, the amount of dendron on the polymer chain, and their generation on the polymer chain. [5] Characteristics of co-polymers are reflections of monomer composition. In other words, reactivities of monomers during polymerization play important role to determine the boundaries of co-polymer properties.…”

Synthesis of a Redox‐Active Denpol as a Potential Electrode in Rechargeable Organic Batteries

“…less than 28 % for PAQS at 10 C). [12] Faster charge-transfer kinetics of AQ-ter-denpol over PAQS shown in the CVs supports the enhanced rate capability. In addition, the stability of AQter-denpol was guaranteed, as there was no serious decay of capacity during cycling charge and discharge processes (Figure 3 d).…”

“…As mentioned above, the crowding effect is presumably the main reason for this general trend. For higher generations, dendrons are compressed and forced away from the backbone, [12] so the steric repulsion thus generated may cause the dendrons close to the chain-end to bend outward, limiting the accessibility to the reacting site. [13] To overcome this, we forced our interest on the more reactive third-generation Grubbs catalyst based on bispyridine complexes.…”

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

“…The synthesis of such dendronized polymers is well established and their characteristics are actively studied, both experimentally and theoretically. Depending on the dendritic content and design of the dendrons, polymers can be highly stretched, collapsed, or everything in between . Similar to polymers grafted with a high density of long linear pendants, such as bottle brush polymers, dendronized polymers are stretched by ample incorporation of sufficiently large dendrons .…”