The conformational phase diagram of neutral polymers in the presence of attractive crowders

• Published in: The Journal of chemical physics Vol. 158; no. 11; p. 114903
• Main Authors: Garg, Hitesh, Rajesh, R, Vemparala, Satyavani
• Format: Journal Article
• Language: English
• Published: United States 21.03.2023
• ISSN: 1089-7690
• DOI: 10.1063/5.0140721

Extensive coarse-grained molecular dynamics simulations are performed to investigate the conformational phase diagram of a neutral polymer in the presence of attractive crowders. We show that, for low crowder densities, the polymer predominantly shows three phases as a function of both intra-polymer and polymer-crowder interactions: (1) weak intra-polymer and weak polymer-crowder attractive interactions induce extended or coil polymer conformations (phase E), (2) strong intra-polymer and relatively weak polymer-crowder attractive interactions induce collapsed or globular conformations (phase CI), and (3) strong polymer-crowder attractive interactions, regardless of intra-polymer interactions, induce a second collapsed or globular conformation that encloses bridging crowders (phase CB). The detailed phase diagram is obtained by determining the phase boundaries delineating the different phases based on an analysis of the radius of gyration as well as bridging crowders. The dependence of the phase diagram on strength of crowder-crowder attractive interactions and crowder density is clarified. We also show that when the crowder density is increased, a third collapsed phase of the polymer emerges for weak intra-polymer attractive interactions. This crowder density-induced compaction is shown to be enhanced by stronger crowder-crowder attraction and is different from the depletion-induced collapse mechanism, which is primarily driven by repulsive interactions. We also provide a unified explanation of the observed re-entrant swollen/extended conformations of the earlier simulations of weak and strongly self-interacting polymers in terms of crowder-crowder attractive interactions.