Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes

Yu, Jing; Jackson, Nicholas E.; Xu, Xin; Brettmann, Blair K.; Ruths, Marina; de Pablo, Juan J.; Tirrell, Matthew

doi:10.1126/sciadv.aao1497

Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes

Journal Article · Fri Dec 08 04:00:00 EST 2017 · Science Advances

DOI:https://doi.org/10.1126/sciadv.aao1497· OSTI ID:1476643

^[1]; ^[2]; Xu, Xin ^[3]; ^[4]; ^[3]; de Pablo, Juan J. ^[2]; Tirrell, Matthew ^[2]

Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States); Nanyang Technological Univ. (Singapore)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Massachusetts, Lowell, MA (United States)
Univ. of Chicago, IL (United States); Georgia Inst. of Technology, Atlanta, GA (United States)

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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1476643

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 12 Vol. 3; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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