Application of Monte Carlo simulation in addressing key issues of complex coacervation formed by polyelectrolytes and oppositely charged colloids

Abstract

This paper reviews the recent advance of Monte Carlo (MC) simulation in addressing key issues of complex coacervation between polyelectrolytes and oppositely charged colloids. Readers were first supplied with a brief overview of current knowledge and experimental strategies in the study of complex coacervation. In the next section, the general MC simulation procedures as well as representative strategies applied in complex coacervation were summarized. The unique contributions of MC simulation in either capturing delicate features, easing the experimental trials or proving the concept were then elucidated through the following aspects: i) identify phase boundary and decouple interaction contributions; ii) clarify composition distribution and internal structure; iii) predict the influences of physicochemical conditions on complex coacervation; iv) delineate the mechanisms for "binding on the wrong side of the isoelectric point". Finally, current challenges as well as prospects of MC simulation in complex coacervation are also discussed. The ultimate goal of this review is to provide readers with basic guideline for synergistic design of experiments in combination with MC simulation, and deliver convincing interpretation and reliable prediction for the structure and behavior in polyelectrolyte-macroion complex coacervation.

Keywords: Complex coacervation; Electrostatic interaction; Macroion; Monte Carlo simulation; Polyelectrolyte.