Ions effect on tunable coacervate and its relevance to the Hofmeister series

Ion induced self-assembly allows a better understanding of the natural self-assemblies such as proteins, colloids and polymers, etc. However, little is known about ions mediated tunable coacervates. Herein, we show that the Hofmeister series of ions can be used to explain the tunable coacervates induced by different types of ions. The assembly of benzenesulfonate and polyetheramine undergoes the transformation from bilayer vesicles to the network structure of bottom coacervate with the increased concentration of inorganic salt, and the tunable coacervates of surfactants was found to be highly dependent on the ion species in solution. The affinity and compatibility of cations and surfactant follows Li+ > Na+ > K+, which determines the disturbance range of water molecules in the hydration shell of surfactant, resulting in different states of the final aggregates varying from precipitate, upper coacervate to bottom coacervate. The chaotropic anions (e.g., I−) have more pronounced dehydration effect on surfactants compared with kosmotropic anions (e.g., F−), and the ability of anions induced the transition from the bottom to the upper coacervate follows I−> Br− > Cl− >F−. Since the structural transformation of bottom coacervate requires conformational entropy, the release of water molecules is thermodynamically favorable for the transition of coacervates, which is also verified by the fact that the occurrence of dehydration drives the bottom coacervate upward to the upper coacervate during the heating process. These results provide a close link between the Hofmeister series and the controllable coacervates, which is of importance for further progress in ion specificity effects and creates a basic physicochemistry skeleton to understand this important phenomenon. [Display omitted]