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Title: Phase Behavior and Salt Partitioning in Polyelectrolyte Complex Coacervates

Polyelectrolyte complexes are omnipresent both in nature and in the technological world, including nucleotide condensates, biological marine adhesives, food stabilizers, encapsulants, and carriers for gene therapy. However, the true phase behavior of complexes, resulting from associative phase separation of oppositely charged polyelectrolytes, remains poorly understood. Here in this study, we rely on complementary experimental and simulation approaches to create a complete quantitative description of the phase behavior of polyelectrolyte complexes that represents a significant advance in our understanding of the underlying physics of polyelectrolyte complexation. Experiments employing multiple approaches with model polyelectrolytes oppositely charged polypeptides poly(L-lysine) and poly(D,Lglutamic acid) of matched chain lengths led to phase diagrams with compositions of the complex and the supernatant that were in excellent agreement with simulation results. Contrary to the widely accepted theory for complexation, we found preferential partitioning of salt ions into the supernatant phase. Additionally, the salt partitioning into the supernatant phase was found to initially increase and then decrease on increasing the salt concentrations, manifesting as a distinct minimum in the salt partition coefficients. These trends were shown by simulations to be strongly influenced by the excluded volume interactions in the complex phase, which were not accounted for in their entiretymore » in earlier theories. Finally, we believe the comprehensive data we present will be conducive to the development of an accurate physical theory for polyelectrolyte complexation with predictive capabilities.« less
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [1] ;  [3] ; ORCiD logo [3] ;  [3]
  1. Univ. of Chicago, IL (United States)
  2. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of California, Los Angeles, CA (United States)
  3. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 8; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE; National Institute of Standards and Technology (NIST) - Center for Hierarchical Materials Design (CHiMaD)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1482176

Li, Lu, Srivastava, Samanvaya, Andreev, Marat, Marciel, Amanda B., de Pablo, Juan J., and Tirrell, Matthew V.. Phase Behavior and Salt Partitioning in Polyelectrolyte Complex Coacervates. United States: N. p., Web. doi:10.1021/acs.macromol.8b00238.
Li, Lu, Srivastava, Samanvaya, Andreev, Marat, Marciel, Amanda B., de Pablo, Juan J., & Tirrell, Matthew V.. Phase Behavior and Salt Partitioning in Polyelectrolyte Complex Coacervates. United States. doi:10.1021/acs.macromol.8b00238.
Li, Lu, Srivastava, Samanvaya, Andreev, Marat, Marciel, Amanda B., de Pablo, Juan J., and Tirrell, Matthew V.. 2018. "Phase Behavior and Salt Partitioning in Polyelectrolyte Complex Coacervates". United States. doi:10.1021/acs.macromol.8b00238. https://www.osti.gov/servlets/purl/1482176.
@article{osti_1482176,
title = {Phase Behavior and Salt Partitioning in Polyelectrolyte Complex Coacervates},
author = {Li, Lu and Srivastava, Samanvaya and Andreev, Marat and Marciel, Amanda B. and de Pablo, Juan J. and Tirrell, Matthew V.},
abstractNote = {Polyelectrolyte complexes are omnipresent both in nature and in the technological world, including nucleotide condensates, biological marine adhesives, food stabilizers, encapsulants, and carriers for gene therapy. However, the true phase behavior of complexes, resulting from associative phase separation of oppositely charged polyelectrolytes, remains poorly understood. Here in this study, we rely on complementary experimental and simulation approaches to create a complete quantitative description of the phase behavior of polyelectrolyte complexes that represents a significant advance in our understanding of the underlying physics of polyelectrolyte complexation. Experiments employing multiple approaches with model polyelectrolytes oppositely charged polypeptides poly(L-lysine) and poly(D,Lglutamic acid) of matched chain lengths led to phase diagrams with compositions of the complex and the supernatant that were in excellent agreement with simulation results. Contrary to the widely accepted theory for complexation, we found preferential partitioning of salt ions into the supernatant phase. Additionally, the salt partitioning into the supernatant phase was found to initially increase and then decrease on increasing the salt concentrations, manifesting as a distinct minimum in the salt partition coefficients. These trends were shown by simulations to be strongly influenced by the excluded volume interactions in the complex phase, which were not accounted for in their entirety in earlier theories. Finally, we believe the comprehensive data we present will be conducive to the development of an accurate physical theory for polyelectrolyte complexation with predictive capabilities.},
doi = {10.1021/acs.macromol.8b00238},
journal = {Macromolecules},
number = 8,
volume = 51,
place = {United States},
year = {2018},
month = {4}
}