Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent

Abstract The formation of coacervates through phase separation of oppositely charged polyelectrolytes (PEs) is critical for understanding biological condensates and developing responsive materials. Traditionally, coacervates are viewed as spherical droplets with growth dynamics resembling liquid-liq...

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Main Authors: Jiaxing Yuan, Hajime Tanaka
Format: Article
Language:English
Published: Nature Portfolio 2025-02-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-56583-6
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author Jiaxing Yuan
Hajime Tanaka
author_facet Jiaxing Yuan
Hajime Tanaka
author_sort Jiaxing Yuan
collection DOAJ
description Abstract The formation of coacervates through phase separation of oppositely charged polyelectrolytes (PEs) is critical for understanding biological condensates and developing responsive materials. Traditionally, coacervates are viewed as spherical droplets with growth dynamics resembling liquid-liquid phase separation. However, our fluid particle dynamics simulations incorporating hydrodynamic and electrostatic interactions challenge this perspective. Here, we find that oppositely charged PEs form a percolated network even in semi-dilute solutions, coarsening with a unique growth law, ℓ ∝ t 1/2. This self-similarity, absent for neutral polymers in poor solvents, arises because PEs in good solvents exhibit weaker, longer-range attractions due to spatial charge inhomogeneity under global charge neutrality. This results in a lower density of the PEs-rich phase and reduced interfacial tension. Increased charge asymmetry further slows network coarsening. Additionally, coacervate droplets initially display irregular shapes due to weak interfacial tension, transitioning slowly to spherical forms. Our research provides new insights into coacervate morphology and coarsening dynamics.
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spelling doaj-art-baf0f4bfc3f34afb91d11ce0dcff73d32025-08-20T03:00:58ZengNature PortfolioNature Communications2041-17232025-02-0116111410.1038/s41467-025-56583-6Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solventJiaxing Yuan0Hajime Tanaka1Advanced Materials Thrust, Function Hub, The Hong Kong University of Science and Technology (Guangzhou)Research Center for Advanced Science and Technology, University of TokyoAbstract The formation of coacervates through phase separation of oppositely charged polyelectrolytes (PEs) is critical for understanding biological condensates and developing responsive materials. Traditionally, coacervates are viewed as spherical droplets with growth dynamics resembling liquid-liquid phase separation. However, our fluid particle dynamics simulations incorporating hydrodynamic and electrostatic interactions challenge this perspective. Here, we find that oppositely charged PEs form a percolated network even in semi-dilute solutions, coarsening with a unique growth law, ℓ ∝ t 1/2. This self-similarity, absent for neutral polymers in poor solvents, arises because PEs in good solvents exhibit weaker, longer-range attractions due to spatial charge inhomogeneity under global charge neutrality. This results in a lower density of the PEs-rich phase and reduced interfacial tension. Increased charge asymmetry further slows network coarsening. Additionally, coacervate droplets initially display irregular shapes due to weak interfacial tension, transitioning slowly to spherical forms. Our research provides new insights into coacervate morphology and coarsening dynamics.https://doi.org/10.1038/s41467-025-56583-6
spellingShingle Jiaxing Yuan
Hajime Tanaka
Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent
Nature Communications
title Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent
title_full Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent
title_fullStr Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent
title_full_unstemmed Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent
title_short Network-forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent
title_sort network forming phase separation of oppositely charged polyelectrolytes forming coacervates in a solvent
url https://doi.org/10.1038/s41467-025-56583-6
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