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Title: Structure of Polyelectrolyte Brushes in the Presence of Multivalent Counterions

Journal Article · · Macromolecules
 [1];  [2];  [3];  [4];  [5];  [1];  [1]
  1. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Univ. of Akron, OH (United States). Dept. of Polymer Engineering
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Polyelectrolyte brushes are of great importance to a wide range of fields, ranging from colloidal stabilization to responsive and tunable materials to lubrication. Here, we synthesized high-density polystyrenesulfonate (PSS) brushes using surface initiated atom transfer radical polymerization and performed neutron reflectivity (NR) and surface force measurements using a surface forces apparatus (SFA) to investigate the effect of monovalent Na+, divalent Ca2+, Mg2+, and Ba2+, and trivalent Y3+ counterions on the structure of the PSS brushes. NR and SFA results demonstrate that in monovalent salt solution the behavior of the PSS brushes agrees with scaling theory well, exhibiting two distinct regimes: the osmotic and salted brush regimes. Introducing trivalent Y3+ cations causes an abrupt shrinkage of the PSS brush due to the uptake of Y3+ counterions. The uptake of Y3+ counterions and shrinkage of the brush are reversible upon increasing the concentration of monovalent salt. Divalent cations, Mg2+, Ca2+, and Ba2+, while all significantly affecting the structure of PSS brushes, show strong ion specific effects that are related to the specific interactions between the divalent cations and the sulfonate groups. Our results demonstrate that the presence of multivalent counterions, even at relatively low concentrations, can strongly affect the structure of polyelectrolyte brushes. Finally, the results also highlight the importance of ion specificity to the structure of polyelectrolyte brushes in solution.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1352620
Journal Information:
Macromolecules, Vol. 49, Issue 15; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 79 works
Citation information provided by
Web of Science

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Polyamidoxime chain length drives emergent metal-binding phenomena journal January 2019
Explicit Ion Effects on the Charge and Conformation of Weak Polyelectrolytes journal January 2019
Structure and Functionality of Polyelectrolyte Brushes: A Surface Force Perspective journal October 2018
Single-stranded DNA oligomer brush structure is dominated by intramolecular interactions mediated by the ion environment journal January 2018
Morphologies of a polyelectrolyte brush grafted onto a cubic colloid in the presence of trivalent ions journal January 2019
Long-Range Hydrophilic Attraction between Water and Polyelectrolyte Surfaces in Oil journal October 2016
Self-assembly of polyelectrolyte diblock copolymers at monovalent and multivalent counterions journal January 2019
Multivalent counterions accumulate in star-like polyelectrolytes and collapse the polymer in spite of increasing its ionization journal January 2020
Salt type and concentration affect the viscoelasticity of polyelectrolyte solutions journal May 2018
An in situ shearing x-ray measurement system for exploring structures and dynamics at the solid–liquid interface journal January 2020
Removal of metal ions and humic acids through polyetherimide membrane with grafted bentonite clay journal March 2018
Quantifying Mg2+ Binding to ssDNA Oligomers: A Self-Consistent Field Theory Study at Varying Ionic Strengths and Grafting Densities journal December 2018
Long-Range Hydrophilic Attraction between Water and Polyelectrolyte Surfaces in Oil journal October 2016
Removal of metal ions and humic acids through polyetherimide membrane with grafted bentonite clay journal March 2018
Quantifying Mg2+ Binding to ssDNA Oligomers: A Self-Consistent Field Theory Study at Varying Ionic Strengths and Grafting Densities journal December 2018
Explicit Ion Effects on the Charge and Conformation of Weak Polyelectrolytes journal January 2019