Controlling composition of coexisting phases via molecular transitions

Abstract: Phase separation and transitions among different molecular states are ubiquitous in living cells. Such transitions can be governed by local equilibrium thermodynamics or by active processes controlled by biological fuel. It remains largely unexplored how the behavior of phase-separating systems with molecular transitions differs between thermodynamic equilibrium and cases where detailed balance of the molecular transition rates is broken due to the presence of fuel. Here, we present a model of a phase-separating ternary mixture where two components can convert into each other. At thermodynamic equilibrium, we find that molecular transitions can give rise to a lower dissolution temperature and thus reentrant phase behavior. Moreover, we find a discontinuous thermodynamic phase transition in the composition of the droplet phase if both converting molecules attract themselves with similar interaction strength. Breaking detailed-balance of the molecular transition leads to quasi-discontinuous changes in droplet composition by varying the fuel amount for a larger range of inter-molecular interactions. Our findings showcase that phase separation with molecular transitions provides a versatile mechanism to control properties of intra-cellular and synthetic condensates via discontinuous switches in droplet composition.