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Title: Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes

Subtle details about a polyelectrolyte’s surrounding environment can dictate its structural features and potential applications. Atomic force microscopy (AFM), surface forces apparatus (SFA) measurements, and coarse-grained molecular dynamics simulations are combined to study the structure of planar polyelectrolyte brushes [poly(styrenesulfonate), PSS] in a variety of solvent conditions. More specifically, AFM images provide a first direct visualization of lateral inhomogeneities on the surface of polyelectrolyte brushes collapsed in solutions containing trivalent counterions. These images are interpreted in the context of a coarse-grained molecular model and are corroborated by accompanying interaction force measurements with the SFA. Our findings indicate that lateral inhomogeneities are absent from PSS brush layers collapsed in a poor solvent without multivalent ions. Together, AFM, SFA, and our molecular model present a detailed picture in which solvophobic and multivalent ion–induced effects work in concert to drive strong phase separation, with electrostatic bridging of polyelectrolyte chains playing an essential role in the collapsed structure formation.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [3] ; ORCiD logo [4] ; ORCiD logo [3] ;  [2] ;  [2]
  1. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States); Nanyang Technological Univ. (Singapore)
  2. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Univ. of Massachusetts, Lowell, MA (United States)
  4. Univ. of Chicago, IL (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 12; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING
OSTI Identifier:
1476643

Yu, Jing, Jackson, Nicholas E., Xu, Xin, Brettmann, Blair K., Ruths, Marina, de Pablo, Juan J., and Tirrell, Matthew. Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes. United States: N. p., Web. doi:10.1126/sciadv.aao1497.
Yu, Jing, Jackson, Nicholas E., Xu, Xin, Brettmann, Blair K., Ruths, Marina, de Pablo, Juan J., & Tirrell, Matthew. Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes. United States. doi:10.1126/sciadv.aao1497.
Yu, Jing, Jackson, Nicholas E., Xu, Xin, Brettmann, Blair K., Ruths, Marina, de Pablo, Juan J., and Tirrell, Matthew. 2017. "Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes". United States. doi:10.1126/sciadv.aao1497. https://www.osti.gov/servlets/purl/1476643.
@article{osti_1476643,
title = {Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes},
author = {Yu, Jing and Jackson, Nicholas E. and Xu, Xin and Brettmann, Blair K. and Ruths, Marina and de Pablo, Juan J. and Tirrell, Matthew},
abstractNote = {Subtle details about a polyelectrolyte’s surrounding environment can dictate its structural features and potential applications. Atomic force microscopy (AFM), surface forces apparatus (SFA) measurements, and coarse-grained molecular dynamics simulations are combined to study the structure of planar polyelectrolyte brushes [poly(styrenesulfonate), PSS] in a variety of solvent conditions. More specifically, AFM images provide a first direct visualization of lateral inhomogeneities on the surface of polyelectrolyte brushes collapsed in solutions containing trivalent counterions. These images are interpreted in the context of a coarse-grained molecular model and are corroborated by accompanying interaction force measurements with the SFA. Our findings indicate that lateral inhomogeneities are absent from PSS brush layers collapsed in a poor solvent without multivalent ions. Together, AFM, SFA, and our molecular model present a detailed picture in which solvophobic and multivalent ion–induced effects work in concert to drive strong phase separation, with electrostatic bridging of polyelectrolyte chains playing an essential role in the collapsed structure formation.},
doi = {10.1126/sciadv.aao1497},
journal = {Science Advances},
number = 12,
volume = 3,
place = {United States},
year = {2017},
month = {12}
}