Influence of the shape of crowding particles on the structural transitions in a polymer.

We investigate the structural transitions in a polymer induced by spherical and nonspherical crowding particles over a wide range of conditions. The polymer conformations are specified by the radius of gyration and the quality of the solvent in the absence of crowding particles. In the presence of crowding particles, the structures are altered by the volume fraction, size, shape, and polydispersity of the crowders. We show that crowding induces an array of structural changes, ranging from helix, helical hairpin (HH), and multiple helix bundles (HBs), depending on the interplay of multiple length and energy scales including the solvent quality, length of the polymer, temperature, and the characteristics of the crowding agents. In nearly good solvents, the polymer undergoes coil-helix transition in accord with the predictions based on the entropic stabilization mechanism. Higher-order (HH and HB) structures are obtained in poor or moderately poor solvents. In a binary mixture of spherical crowders, the effect of the two components is largely additive with the polymer undergoing greater compaction at higher volume fraction. In contrast to spherical crowders, spherocylinder-like crowders have a dramatically different effect on the diagram of states of the polymer. In the presence of spherocylinders, the polymer prefers to form a nearly ideal helix, especially at low temperatures and high aspect ratios of the crowders, at volume fractions that are not large enough for nematic order. Surprisingly, there is a complete absence of HH and HB in the range of conditions explored here. The dominant formation of spherocylinder-induced helix formation is due to the tendency of the spherocylinders and the polymer to align along the director formed by an increase in nematic order only in the vicinity of the polymer. Our study, which has produced several testable predictions, shows that only by probing the effects of crowding on a polymer (or a protein and RNA) over a wide range of conditions can the diagram of states be quantitatively described.