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Anomalous Liquid-Liquid Phase Separation Dynamics in Polymerization-Driven Complex Coacervation
Samiksha Shrivastava1, Shensheng Chen1
1Department of Chemical and Biological Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong.
ACS Macro Letters
|June 11, 2026
Summary
Polymerization-driven liquid-liquid phase separation (LLPS) kinetics were computationally studied. This research reveals a two-stage domain growth law, significantly faster than previously predicted models.
Area of Science:
- Biomaterials Science
- Polymer Chemistry
- Soft Matter Physics
Background:
- Liquid-liquid phase separation (LLPS) is crucial for biological processes and biomaterial development.
- The kinetic pathways and domain growth laws governing polymerization-driven LLPS are not well understood.
Purpose of the Study:
- To computationally investigate the dynamics of LLPS in polymerization-driven polyelectrolyte complex coacervation.
- To elucidate the kinetic pathway and domain growth law during polymerization-driven LLPS.
Main Methods:
- Computational modeling of polyelectrolyte complex coacervation.
- Analysis of LLPS dynamics with changing macromolecular charge asymmetry and polymer connectivity during polymerization.
Main Results:
- Identified a two-stage kinetic pathway for domain growth, L(t).
- Observed exponential growth L(t) ~ exp(t) in the early stage due to polymerization-driven collapse.
- Found near-linear scaling L(t) ~ t in the later stage, driven by polymerization-coarsening coupling.
Conclusions:
- Polymerization-driven LLPS exhibits significantly accelerated domain growth kinetics compared to classical theories (L(t) ~ t^(1/3)).
- The study provides new insights into the fundamental mechanisms governing LLPS in complex polymer systems.
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