Structure of Stacked Aggregates of Semiflexible Rings Under Spherical Confinement: A Computational Study.

How ordered and mutually independent are semiflexible ring polymers (RPs) confined to a spherical cavity of variable radius? By varying the cavity radius, we systematically investigate the effect of the confinement size on the conformations of RPs using the coarse-grained molecular dynamics simulations. The results reveal that as the bending energy increases, the RPs exhibit a transition from a purely flexible coil to an elongated oblate-shaped object and, eventually, to a disk-like conformation. Simultaneously, the stacked aggregates composed of adjacent, mutually nearly parallel, semiflexible RPs emerge for stiffer chains. We find that the structural modulation of the stacked aggregates is regulated by the confinement size. For the conditions of strong confinement (R<2Rg, where Rg is the radius of gyration of an RP), the semiflexible RPs undergo peculiar deformations and twisting that lead to disruption of the stacked aggregates. At R≈2Rg, the average number of the RPs per stack reaches a maximum. Concurrently, the order of spatial alignment of all semiflexible RPs is maximized with the global orientational-order parameter reaching the value S≈0.79. As the cavity radius further increases, at R>3Rg, the semiflexible RPs gain greater mobility resulting in diverse orientations of the aggregates being formed, with the order parameter dropping to S≈0.05. These findings provide important quantitative insights for future applications of the RPs, i.e., in micro- and nanodevice assembly.