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

Ylitalo, Andrew S. and Balzer, Christopher and Zhang, Pengfei and Wang, Zhen-Gang (2021) Electrostatic Correlations and Temperature-Dependent Dielectric Constant Can Model LCST in Polyelectrolyte Complex Coacervation. Macromolecules, 54 (24). pp. 11326-11337. ISSN 0024-9297. doi:10.1021/acs.macromol.1c02000.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription
Ylitalo, Andrew S.0000-0003-4086-3508
Balzer, Christopher0000-0002-9767-8437
Zhang, Pengfei0000-0002-4226-1394
Wang, Zhen-Gang0000-0002-3361-6114
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.
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1745301
Department of Energy (DOE)DE-SC0020347
National Natural Science Foundation of China21803011
National Natural Science Foundation of China22073016
Hong Kong Quantum AI Lab Ltd.UNSPECIFIED
Subject Keywords:Salts, Electrostatics, Electrical properties, Phase transitions, Polyelectrolytes
Issue or Number:24
Record Number:CaltechAUTHORS:20211221-866875000
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Official Citation:Electrostatic Correlations and Temperature-Dependent Dielectric Constant Can Model LCST in Polyelectrolyte Complex Coacervation. Andrew S. Ylitalo, Christopher Balzer, Pengfei Zhang, and Zhen-Gang Wang. Macromolecules 2021 54 (24), 11326-11337; DOI: 10.1021/acs.macromol.1c02000
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112617
Deposited By: George Porter
Deposited On:21 Dec 2021 23:41
Last Modified:03 Jan 2022 22:12

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