Polyelectrolyte Complex Coacervation across a Broad Range of Charge Densities

Neitzel, Angelika E.; Fang, Yan N.; Yu, Boyuan; Rumyantsev, Artem M.; de Pablo, Juan J.; Tirrell, Matthew V.

doi:10.1021/acs.macromol.1c00703

Title: Polyelectrolyte Complex Coacervation across a Broad Range of Charge Densities

Journal Article · Tue Jul 06 00:00:00 EDT 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c00703· OSTI ID:1815825

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Univ. of Chicago, IL (United States). Pritzker School of Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Univ. of Chicago, IL (United States). Pritzker School of Molecular Engineering

Polyelectrolyte complex coacervates of homologous (co)polyelectrolytes with a near-ideally random distribution of a charged and neutral ethylene oxide comonomer were synthesized. The unique platform provided by these building blocks enabled an investigation of the phase behavior across charge fractions 0.10 ≤ f ≤ 1.0. Experimental phase diagrams for f = 0.30–1.0 were obtained from thermogravimetric analysis of complex and supernatant phases and contrasted with molecular dynamics simulations and theoretical scaling laws. At intermediate to high f, a dependence of polymer weight fraction in the salt-free coacervate phase (w_P,c) of w_P,c ~ f^0.37±0.01 was extracted; this trend was in good agreement with accompanying simulation predictions. Below f = 0.50, w_P,c was found to decrease more dramatically, qualitatively in line with theory and simulations predicting an exponent of 2/3 at f ≤ 0.25. Preferential salt partitioning to either coacervate or supernatant was found to be dictated by the chemistry of the constituent (co)polyelectrolytes.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF); National Institute of Standards and Technology (NIST), Center for Hierarchical Materials Design (CHiMaD)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1815825

Alternate ID(s):: OSTI ID: 1868968

Journal Information:: Macromolecules, Vol. 54, Issue 14; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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