Unveiling the Electrostatically Driven Collapsing and Relaxation of Polyelectrolyte–Colloid Complexes: A Tunable Pathway to Colloidal Assembly

Polyelectrolyte-colloid (PEC) complexes, ubiquitous across diverse fields, exhibit remarkable phase transitions, mimicking intricate biological assemblies. While the role of electrostatic forces in the PEC complex assembly is undeniable, achieving a holistic comprehension remains an elusive goal. This study unveils a fascinating phenomenon: the formation of highly collapsed coacervate structures in PEC complexes at elevated polyelectrolyte concentrations, followed by the swelling of complexes at even higher concentrations. Employing anionic silica colloids and cationic chitosan as a model system, small-angle X-ray/neutron (SAXS/SANS) elucidates the transition from a bead-on-a-necklace-like phase to a dense packed coacervate state (with volume fraction ∼0.62) until 3 wt % concentration of the polyelectrolyte. However, beyond 3 wt %, swelling of the dense collapsed assembly is observed. This structural evolution of PEC complexes as a function of chitosan concentration is attributed to the interplay of electrostatically driven interactions and the Donnan effect. Notably, the critical concentration for coacervation,