Small ion effects on self-coacervation phenomena in block polyampholytes

Self-coacervation is a phenomenon in which a solution of polyampholytes spontaneously phase separates into a dense liquid coacervate phase, rich in the polyampholyte, coexisting with a dilute supernatant phase. Such coacervation results in the formation of membraneless organelles in vivo and has further been applied industrially as synthetic encapsulants and coatings. It has been suggested that coacervation is primarily driven by the entropy gain from releasing counter-ions upon complexation. Using fully fluctuating field-theoretic simulations employing complex Langevin sampling and complementary molecular dynamics simulations, we have determined that the small ions contribute only weakly to the self-coacervation behavior of charge-symmetric block polyampholytes in solution. Salt partitioning between the supernatant and coacervate is also found to be negligible in the weak-binding regime at low electrostatic strengths. Asymmetries in charge distribution along the polyampholytes can cause net-charges that lead to "tadpole" configurations in dilute solution and the suppression of phase separation at low salt content. The field and particle-based simulation results are compared with analytical predictions from the random phase approximation (RPA) and postulated scaling relationships. The qualitative trends are mostly captured by the RPA, but the approximation fails at low concentration.