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Title: Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions

Abstract

We provide a theoretical model for the collapse of polyelectrolyte brushes in the presence of multivalent ions, focusing on the formation of lateral inhomogeneties in the collapsed state. Polyelectrolyte brushes are important in a variety of applications, including stabilizing colloidal particles and lubricating surfaces. Many uses rely on the extension of the densely grafted polymer chains from the surface in the extended brush morphology. In the presence Extended Brush of multivalent ions, brushes are significantly shorter than in monovalent ionic solutions, which greatly affects their properties. We base our theoretical analysis on an analogous collapse of polyelectrolyte brushes in a poor solvent, providing an energy balance representation for pinned micelles and cylindrical bundles. The equilibrium brush heights predicted for these structures are of a similar magnitude to those measured experimentally. The formation of lateral structures can open new avenues for stimuli-responsive applications that rely on nanoscale pattern formation on surfaces.

Authors:
ORCiD logo [1];  [2];  [3]
  1. The Institute for Molecular Engineering, The University of Chicago, 5640 S. Ellis Ave., Chicago, Illinois 60637, United States
  2. Materials Department, Room 3004 Materials Research Laboratory, University of California, Santa Barbara, Santa Barbara, California 93106, United States
  3. The Institute for Molecular Engineering, The University of Chicago, 5640 S. Ellis Ave., Chicago, Illinois 60637, United States; The Institute for Molecular Engineering, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1420326
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Macromolecules; Journal Volume: 50; Journal Issue: 3
Country of Publication:
United States
Language:
English

Citation Formats

Brettmann, Blair, Pincus, Philip, and Tirrell, Matthew. Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions. United States: N. p., 2017. Web. doi:10.1021/acs.macromol.6b02563.
Brettmann, Blair, Pincus, Philip, & Tirrell, Matthew. Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions. United States. doi:10.1021/acs.macromol.6b02563.
Brettmann, Blair, Pincus, Philip, and Tirrell, Matthew. Fri . "Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions". United States. doi:10.1021/acs.macromol.6b02563.
@article{osti_1420326,
title = {Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions},
author = {Brettmann, Blair and Pincus, Philip and Tirrell, Matthew},
abstractNote = {We provide a theoretical model for the collapse of polyelectrolyte brushes in the presence of multivalent ions, focusing on the formation of lateral inhomogeneties in the collapsed state. Polyelectrolyte brushes are important in a variety of applications, including stabilizing colloidal particles and lubricating surfaces. Many uses rely on the extension of the densely grafted polymer chains from the surface in the extended brush morphology. In the presence Extended Brush of multivalent ions, brushes are significantly shorter than in monovalent ionic solutions, which greatly affects their properties. We base our theoretical analysis on an analogous collapse of polyelectrolyte brushes in a poor solvent, providing an energy balance representation for pinned micelles and cylindrical bundles. The equilibrium brush heights predicted for these structures are of a similar magnitude to those measured experimentally. The formation of lateral structures can open new avenues for stimuli-responsive applications that rely on nanoscale pattern formation on surfaces.},
doi = {10.1021/acs.macromol.6b02563},
journal = {Macromolecules},
number = 3,
volume = 50,
place = {United States},
year = {Fri Jan 13 00:00:00 EST 2017},
month = {Fri Jan 13 00:00:00 EST 2017}
}
  • Here, coarse-grained molecular dynamics enhanced by free-energy sampling methods is used to examine the roles of solvophobicity and multivalent salts on polyelectrolyte brush collapse. Specifically, we demonstrate that while ostensibly similar, solvophobic collapsed brushes and multivalent-ion collapsed brushes exhibit distinct mechanistic and structural features. Notably, multivalent-induced heterogeneous brush collapse is observed under good solvent polymer backbone conditions, demonstrating that the mechanism of multivalent collapse is not contingent upon a solvophobic backbone. Umbrella sampling of the potential of mean-force (PMF) between two individual brush strands confirms this analysis, revealing starkly different PMFs under solvophobic and multivalent conditions, suggesting the role ofmore » multivalent “bridging” as the discriminating feature in trivalent collapse. Structurally, multivalent ions show a propensity for nucleating order within collapsed brushes, whereas poor-solvent collapsed brushes are more disordered; this difference is traced to the existence of a metastable PMF minimum for poor solvent conditions, and a global PMF minimum for trivalent systems, under experimentally relevant conditions.« less
  • 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 Ca 2+, Mg 2+, and Ba 2+, and trivalent Y 3+ 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 theorymore » well, exhibiting two distinct regimes: the osmotic and salted brush regimes. Introducing trivalent Y 3+ cations causes an abrupt shrinkage of the PSS brush due to the uptake of Y 3+ counterions. The uptake of Y 3+ counterions and shrinkage of the brush are reversible upon increasing the concentration of monovalent salt. Divalent cations, Mg 2+, Ca 2+, and Ba 2+, 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.« less
  • Applications of end-tethered polyelectrolyte “brushes” to modify solid surfaces have been developed and studied for their colloidal stabilization and high lubrication properties. Current efforts have expanded into biological realms and stimuli-responsive materials. Our work explores responsive and reversible aspects of polyelectrolyte brush behavior when polyelectrolyte chains interact with oppositely charged multivalent ions and complexes, which act as counterions. There is a significant void in the polyelectrolyte literature regarding interactions with multivalent species. This paper demonstrates that interactions between solid surfaces bearing negatively charged polyelectrolyte brushes are highly sensitive to the presence of trivalent lanthanum, La3+. Lanthanum cations have unique interactionsmore » with polyelectrolyte chains, in part due to their small size and hydration radius which results in a high local charge density. Using La3+ in conjunction with the surface forces apparatus (SFA), adhesion has been observed to reversibly appear and disappear upon the uptake and release, respectively, of these multivalent cations acting as counterions. In media of fixed ionic strength set by monovalent sodium salt, at I0 = 0.003 M and I0 = 0.3 M, the sign of the interaction forces between overlapping brushes changes from repulsive to attractive when La3+ concentrations reach 0.1 mol % of the total ion concentration. These results are also shown to be generally consistent with, but subtlety different from, previous polyelectrolyte brush experiments using trivalent ruthenium hexamine in the role of the multivalent counterion.« less
  • Surface tethered polyelectrolyte brushes are scientifically interesting and technologically relevant to many applications, ranging from colloidal stabilization to responsive and tunable materials to lubrication. Many applications operate in environments containing multi-valent ions, media in which our scientific understanding is not yet well-developed. In this paper, we synthesized high-density polystyrene sulfonate (PSS) brushes via surface initiated atom-transfer radical polymerization, and performed neutron reflectivity (NR) measurements to investigate and compare the effects of mono-valent Rb + and tri-valent Y 3+ counterions to the structure of the densely tethered PSS brushes. Our NR results show that in mono-valent RbNO 3 solution, the densemore » PSS brush retained its full thickness up to a salt concentration of 1 M, whereas it immediately collapsed upon adding 1.67 mM of tri-valent Y 3+. Increasing the concentration of Y 3+ beyond this level did not lead to any significant further structure change of the PSS brush. Finally, our findings demonstrate that the presence of multi-valent counterions can significantly alter the structure of polyelectrolyte brushes, in a manner different from mono-valent ions, which has implications for the functionality of the brushes.« less