Mesoscale modelling of polyelectrolyte electrophoresis

TL;DR

This study uses a mesoscopic simulation approach to model the electrophoretic behavior of polyelectrolytes, demonstrating the importance of hydrodynamic interactions and accurately matching experimental results across a wide length scale.

Contribution

It introduces a coarse-grained molecular dynamics and Lattice Boltzmann model that effectively captures polyelectrolyte electrophoresis physics without detailed chemical modeling.

Findings

Hydrodynamic interactions are crucial for electrophoretic motion.

The model accurately reproduces experimental mobility measurements.

Electrostatic and hydrodynamic effects dominate over chemical details.

Abstract

The electrophoretic behaviour of flexible polyelectrolyte chains ranging from single monomers up to long fragments of hundred repeat units is studied by a mesoscopic simulation approach. Abstracting from the atomistic details of the polyelectrolyte and the fluid, a coarse-grained molecular dynamics model connected to a mesoscopic fluid described by the Lattice Boltzmann approach is used to investigate free-solution electrophoresis. Our study demonstrates the importance of hydrodynamic interactions for the electrophoretic motion of polyelectrolytes and quantifies the influence of surrounding ions. The length-dependence of the electrophoretic mobility can be understood by evaluating the scaling behavior of the effective charge and the effective friction. The perfect agreement of our results with experimental measurements shows that all chemical details and fluid structure can be safely neglected, and a suitable coarse-grained approach can yield an accurate description of the physics of the problem, provided that electrostatic and hydrodynamic interactions between all entities in the system, i.e., the polyelectrolyte, dissociated counterions, additional salt and the solvent, are properly accounted for. Our model is able to bridge the single molecule regime of a few nm up to macromolecules with contour lengths of more than 100 nm, a length scale that is currently not accessible to atomistic simulations.