Bridging Field Theory and Ion Pairing in the Modeling of Polyelectrolytes and Complex CoacervationClick to copy article linkArticle link copied!
- Charles E. Sing*Charles E. Sing*Email: [email protected]Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, Illinois 61801, United StatesMore by Charles E. Sing
- Jian QinJian QinDepartment of Chemical Engineering, Stanford University, Stanford, California 94305, United StatesMore by Jian Qin
Abstract
Complex coacervation is a phase separation phenomenon driven by the electrostatic attraction between oppositely charged macromolecular species. A recent surge of interest in coacervation between polyelectrolytes has been driven by both fundamental advances in experimental characterization of these systems and recognition of their relevance for both biological systems such as biomolecular condensates as well as industrially relevant consumer products. Concomitantly, there have been several theories capable of predicting complex coacervation that are used to explain these experimental observations. While there has been a general conceptual consensus on the underlying physics of coacervation, these theoretical approaches have so far remained distinct. Polymer field theory, liquid state theory, ion pairing theories, and scaling theories all provide useful insights, but how the assumptions of each candidate theory are interrelated remains largely unexplored. In this paper, we attempt to show how two such classes of models can be derived from a single starting point using cluster expansions as the basis for discussing which interactions are included in both field theory and ion pairing theory. This allows us to compare and contrast these approaches, evaluate conditions where each model should be relevant, and suggest ways in which existing models can be improved or parameterized.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 11 publications.
- Chao Duan, Rui Wang. Ion Correlation-Driven Hysteretic Adhesion and Repulsion between Opposing Polyelectrolyte Brushes. ACS Macro Letters 2024, 13
(9)
, 1127-1132. https://doi.org/10.1021/acsmacrolett.4c00426
- Julia D. Smith, Ri Chen, Nicolas Noriega Osores, Padma Gopalan. Porous Morphology of High Grafting Density Mixed Polyelectrolyte Brushes Grown from a Y-Inimer Coating. Langmuir 2024, 40
(20)
, 10623-10633. https://doi.org/10.1021/acs.langmuir.4c00556
- Michael Beckinghausen, Andrew J. Spakowitz. Exploration of Phase Behavior in Asymmetric Semiflexible Polyelectrolyte Mixtures Using Polymer Field Theory. Macromolecules 2024, 57
(5)
, 2505-2519. https://doi.org/10.1021/acs.macromol.3c02197
- Moreno Ascani, Gabriele Sadowski, Christoph Held. Molecular thermodynamics of complex coacervate systems. Part I: Modeling of polyelectrolyte solutions using pePC-SAFT. Fluid Phase Equilibria 2025, 591 , 114304. https://doi.org/10.1016/j.fluid.2024.114304
- Moreno Ascani, Wojciech P. Lipínski, Iris B.A. Smokers, Piramsuya Neethirajah, Max Vogel, Evan Spruijt, Gabriele Sadowski, Christoph Held. Molecular thermodynamics of complex coacervate systems. Part II: Measuring and modeling of the phase envelope using pePC-SAFT. Fluid Phase Equilibria 2025, 591 , 114305. https://doi.org/10.1016/j.fluid.2024.114305
- Ji Woong Yu, Changsu Yoo, Suchan Cho, Myungeun Seo, YongJoo Kim. Self-assembly of architected macromolecules: Bridging a gap between experiments and simulations. Chemical Physics Reviews 2025, 6
(1)
https://doi.org/10.1063/5.0236427
- Emmit K. Pert, Paul J. Hurst, Robert M. Waymouth, Grant M. Rotskoff. Coacervation drives morphological diversity of mRNA encapsulating nanoparticles. The Journal of Chemical Physics 2025, 162
(7)
https://doi.org/10.1063/5.0235799
- Chao Duan, Nikhil R. Agrawal, Rui Wang. Electrostatic Correlation Augmented Self-Consistent Field Theory and Its Application to Polyelectrolyte Brushes. Physical Review Letters 2025, 134
(4)
https://doi.org/10.1103/PhysRevLett.134.048101
- Atanu Baksi, Hasan Zerze, Aman Agrawal, Alamgir Karim, Gül H. Zerze. The molecular picture of the local environment in a stable model coacervate. Communications Chemistry 2024, 7
(1)
https://doi.org/10.1038/s42004-024-01304-1
- Conner H. Chee, Rotem Benharush, Lexi R. Knight, Jennifer E. Laaser. Segregative phase separation of strong polyelectrolyte complexes at high salt and high polymer concentrations. Soft Matter 2024, 20
(42)
, 8505-8514. https://doi.org/10.1039/D4SM00994K
- Yuanchi Ma, Robert J. S. Ivancic, Jan Obrzut, Debra J. Audus, Vivek M. Prabhu. Effect of cosolvents on the phase separation of polyelectrolyte complexes. Soft Matter 2024, 20
(37)
, 7512-7520. https://doi.org/10.1039/D4SM00903G
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.