The Role of Chemically Innocent Polyanions in Active, Chemically Fueled Complex Coacervate Droplets

Complex coacervation describes the liquid-liquid phase separation of oppositely charged polymers. Active coacervates are droplets in which one of the electrolyte's affinity is regulated by chemical reactions. These droplets are particularly interesting because they are tightly regulated by reaction kinetics. For example, they serve as a model for membraneless organelles that are also often regulated by biochemical transformations such as post-translational modifications. They are also a great protocell model or could be used to synthesize life-they spontaneously emerge in response to reagents, compete, and decay when all nutrients have been consumed. However, the role of the unreactive building blocks, e.g., the polymeric compounds, is poorly understood. Here, we show the important role of the chemically innocent, unreactive polyanion of our chemically fueled coacervation droplets. We show that the polyanion drastically influences the resulting droplets & PRIME; life cycle without influencing the chemical reaction cycle-either they are very dynamic or have a delayed dissolution. Additionally, we derive a mechanistic understanding of our observations and show how additives and rational polymer design help to create the desired coacervate emulsion life cycles. In chemically fueled complex coacervates, the binding affinity of a peptide building block towards a polyanion can be tuned by a chemical reaction cycle. Beyond the kinetics of the reaction cycle, the interaction of the precursor peptide with the polyanion can influence the droplet lifetime significantly. Strong interactions between the peptide and the polyelectrolytes lead to delayed dissolution of the active droplets but can be controlled further.image