Langevin Dynamics Simulations of the Exchange of Complex Coacervate Core Micelles: The Role of Nonelectrostatic Attraction and Polyelectrolyte Length

Complex coacervate core micelles (C3Ms) are promising encapsulators for a wide variety of (bio)molecules. To protect and stabilize their cargo, it is essential to control their exchange dynamics. Yet, to date, little is known about the kinetic stability of C3Ms and the dynamic equilibrium of molecular building blocks with micellar species. Here we study the C3M exchange during the initial micellization by using Langevin dynamics simulations. In this way, we show that charge neutral heterocomplexes consisting of multiple building blocks are the primary mediator for exchange. In addition, we show that the kinetic stability of the C3Ms can be tuned not only by the electrostatic interaction but also by the nonelectrostatic attraction between the polyelectrolytes, the polyelectrolyte length ratio, and the overall polyelectrolyte length. These insights offer new rational design guides to aid the development of new C3M encapsulation strategies.