Depletion-Induced Forces and Crowding in Polymer-Nanoparticle Mixtures: Role of Polymer Shape Fluctuations and Penetrability

TL;DR

This study models polymers as fluctuating penetrable ellipsoids to analyze how shape fluctuations and penetrability influence depletion forces and crowding effects in polymer-nanoparticle mixtures, revealing their impact on thermodynamic behavior.

Contribution

It introduces a novel ellipsoidal polymer model incorporating shape fluctuations and penetrability to study depletion interactions and crowding effects.

Findings

Polymer shape fluctuations significantly affect depletion forces.

Penetrability alters the strength of depletion-induced interactions.

Model predictions align with polymer field and free-volume theories.

Abstract

Depletion forces and macromolecular crowding govern the structure and function of biopolymers in biological cells and the properties of polymer nanocomposite materials. To isolate and analyze the influence of polymer shape fluctuations and penetrability on depletion-induced interactions and crowding by nanoparticles, we model polymers as effective penetrable ellipsoids, whose shapes fluctuate according to the probability distributions of the eigenvalues of the gyration tensor of an ideal random walk. Within this model, we apply Monte Carlo simulation methods to compute the depletion-induced potential of mean force between hard nanospheres and crowding-induced shape distributions of polymers in the protein limit, in which polymer coils can be easily penetrated by smaller nanospheres. By comparing depletion potentials from simulations of ellipsoidal and spherical polymer models with predictions of polymer field theory and free-volume theory, we show that polymer depletion-induced interactions and crowding depend sensitively on polymer shapes and penetrability, with important implications for bulk thermodynamic phase behavior.