Aggregation kinetics of stiff polyelectrolytes in the presence of multivalent salt

TL;DR

This study uses molecular dynamics simulations to investigate how stiff polyelectrolytes like actin aggregate into bundles in multivalent salt solutions, revealing a hierarchical aggregation process driven by diffusion.

Contribution

It provides a detailed kinetic analysis of bundle formation, highlighting the dominant aggregation mode and validating the Smoluchowski formula without fitting parameters.

Findings

Hierarchical cluster formation observed

Aggregation driven primarily by diffusion, no energy barrier

Smoluchowski formula accurately predicts cluster growth

Abstract

Using molecular dynamics simulations, the kinetics of bundle formation for stiff polyelectrolytes such as actin is studied in the solution of multivalent salt. The dominant kinetic mode of aggregation is found to be the case of one end of one rod meeting others at right angle due to electrostatic interactions. The kinetic pathway to bundle formation involves a hierarchical structure of small clusters forming initially and then feeding into larger clusters, which is reminiscent of the flocculation dynamics of colloids. For the first few cluster sizes, the Smoluchowski formula for the time evolution of the cluster size gives a reasonable account for the results of our simulation without a single fitting parameter. The description using Smoluchowski formula provides evidence for the aggregation time scale to be controlled by diffusion, with no appreciable energy barrier to overcome.