Dynamical and conformational behavior of a polymer in a crowded solution

Abstract

We investigate the structure and dynamics of a polymer in a fluid containing mobile spherical colloidal crowders of radius $R$. We compare and contrast the behavior with Langevin dynamics (LD) and lattice--Boltzmann molecular dynamics (LBMD), the latter incorporating long-range hydrodynamic interactions. Both the colloid size relative to the monomer radius $r$ and the volume fraction $\varphi$ are varied to determine how crowding modifies polymer behavior. Increasing volume fraction induces polymer compaction, with the mechanism strongly dependent on the size ratio $R/r$. Small colloids primarily modify the short-wavelength polymer conformation, causing self-avoiding-walk-like behavior to persist to shorter length scales, whereas large colloids reduce the effective long-wavelength Flory exponent, indicating degraded solvent quality consistent with a confinement-blob picture. Polymer diffusion exhibits distinct behavior in LD and LBMD. In LD, diffusion decreases rapidly and depends strongly on $R/r$; a phenomenological scaling involving $\ln (1+R/r)$ captures this size dependence, and additional scaling with $R_g$ reduces scatter, indicating polymer-scale correlations induced by crowding. In contrast, LBMD diffusion follows an effective-medium-like exponential dependence on concentration, governed by hydrodynamic coupling. Rouse-mode analysis identifies three regimes: scaling breakdown at low volume fraction, Zimm-like behavior at intermediate density in both LD and LB, and at high density hydrodynamic screening in LB with confinement-dominated dynamics in LD.

Accepted for publication in The Journal of Chemical Physics