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Published December 28, 2021 | Supplemental Material
Journal Article Open

Electrostatic Correlations and Temperature-Dependent Dielectric Constant Can Model LCST in Polyelectrolyte Complex Coacervation


The ability of polyelectrolytes to condense into a liquidlike, polyelectrolyte-rich phase out of a dilute supernatant phase through complex coacervation has led to fascinating phenomena, such as membraneless organelles and self-assembled capsules for drug delivery. Recent experiments have demonstrated that heating above a lower critical solution temperature (LCST) can drive complex coacervation. Here, we show that a coarse-grained model of electrostatic correlations is sufficient to model an LCST when accounting for the empirical decrease in the dielectric constant of the solvent upon heating. The predictions of the model agree qualitatively with experimental measurements of the compositions of the coexisting coacervate and supernatant phases. The model also achieves modest quantitative agreement with experiments, despite incorporating no other experimental parameters besides the dielectric constant and a fitted length scale. This agreement underscores the important role that can be played by electrostatic correlations in driving complex coacervation above an LCST.

Additional Information

© 2021 American Chemical Society. Received: September 22, 2021; Revised: November 19, 2021; Published: December 15, 2021. The authors express their gratitude to Dr. Yuanchi Ma and Dr. Vivek Prabhu for sharing data and insights from their experimental work and Prof. Joseph Schlenoff for helpful discussion. A.Y. acknowledges support by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1745301. C.B. is supported by the U.S. Department of Energy, Office of Science, Office of Advanced Scientific Computing Research, Department of Energy Computational Science Graduate Fellowship under Award Number DE-SC0020347. P.Z. acknowledges the financial support provided by the National Natural Science Foundation of China (NSFC grant nos. 21803011 and 22073016). Z.-G.W. acknowledges financial support from the Hong Kong Quantum AI Lab Ltd. The authors declare no competing financial interest.

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August 22, 2023
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