Nanostructured Multiphase Condensation of Complex Coacervates in Polymerization-Induced Electrostatic Self-Assembly

Area of Science:

• Polymer Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Complex coacervates are polymers that undergo liquid-liquid phase separation.
• Polymerization-induced electrostatic self-assembly (PIESA) is a method to create complex polymer structures.
• Understanding the dynamic evolution of coacervates in complex environments is crucial.

Purpose of the Study:

• To investigate the formation of nanostructured multiphase condensates of complex coacervates.
• To explore the morphologies generated during liquid-liquid phase separation driven PIESA (LLPS-PIESA).
• To elucidate the role of chain recruitment and intermolecular interactions in condensate evolution.

Main Methods:

• Utilizing liquid-liquid phase separation driven polymerization-induced electrostatic self-assembly (LLPS-PIESA).
• Observing the dynamic evolution of parent droplets into multiphase condensates.
• Analyzing the recruitment of anionic free chains, cationic growing chains, and nascent clusters.
• Investigating the influence of electrostatic and arginine-like salt bridge interactions.

Main Results:

• Demonstrated the formation of nanostructured multiphase condensates from complex coacervates.
• Observed the evolution of parent droplets into diverse morphologies: dandelions, worms, lamellae, vesicles, and vesicle polymers.
• Identified kinetically dictated recruitment of various chain types and clusters as key to condensate formation.
• Highlighted the interplay of electrostatic and salt bridge interactions in driving self-assembly.

Conclusions:

• Complex coacervates can form sophisticated nanostructured multiphase condensates within dynamic LLPS-PIESA systems.
• The observed morphologies are a result of dynamic chain recruitment and specific intermolecular forces.
• This study provides insights into the self-assembly mechanisms of coacervates in evolving aqueous media.