Effect of Dynamically Arrested Domains on the Phase Behavior, Linear Viscoelasticity and Microstructure of Hyaluronic Acid – Chitosan Complex Coacervates

[Image: see text] Complex coacervates make up a class of versatile materials formed as a result of the electrostatic associations between oppositely charged polyelectrolytes. It is well-known that the viscoelastic properties of these materials can be easily altered with the ionic strength of the medium, resulting in a range of materials from free-flowing liquids to gel-like solids. However, in addition to electrostatics, several other noncovalent interactions could influence the formation of the coacervate phase depending on the chemical nature of the polymers involved. Here, the importance of intermolecular hydrogen bonds on the phase behavior, microstructure, and viscoelasticity of hyaluronic acid (HA)–chitosan (CHI) complex coacervates is revealed. The density of intermolecular hydrogen bonds between CHI units increases with increasing pH of coacervation, which results in dynamically arrested regions within the complex coacervate, leading to elastic gel-like behavior. This pH-dependent behavior may be very relevant for the controlled solidification of complex coacervates and thus for polyelectrolyte material design.