Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Ion-Specific Effects of Divalent Ions on the Structure of Polyelectrolyte Brushes

Abstract

Polyelectrolyte brushes consist of charged polymer chains attached on one end to a surface at high densities. They are relevant for many practical applications ranging from biosensors to drug delivery to colloidal stability. Their structure and functionality can be dramatically influenced by multivalent counterions in the solution environment. In this work, the surface forces apparatus (SFA) and atomic force microscopy (AFM) were used to investigate the effects of three alkaline earth divalent cations, Mg2+, Ca2+, and Ba2+, on the structures of polystyrenesulfonate (PSS) brushes tethered to mica and silicon oxide surfaces. While all these ions caused significant shrinkage of the height of the PSS brushes, strong ion-specific effects were observed. Mg2+ and C2+, caused homogeneous shrinkage; Ba2+ led to pinned-micelle like inhomogeneous structures. Isothermal titration calorimetry (ITC) demonstrated that this ion specificity was mainly caused by the difference in binding energy between sulfonate groups and the divalent cations. Considering the abundance of divalent cations in industrial processes, natural environments, and biological systems, the understanding of strong ion-specific effects of divalent counterions is of great importance for theoretical studies and various applications involving polyelectrolytes.

Authors:
 [1];  [2]; ORCiD logo [3];  [2]; ORCiD logo [4]
+ Show Author Affiliations
  1. Nanyang Technological Univ. (Singapore); Univ. of Massachusetts, Lowell, MA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
  3. Univ. of Massachusetts, Lowell, MA (United States)
  4. Nanyang Technological Univ. (Singapore)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1580738
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 35; Journal Issue: 48; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical structure; Counterions; Cations; Polyelectrolytes; Ions

Citation Formats

Xu, Xin, Mastropietro, Dean, Ruths, Marina, Tirrell, Matthew, and Yu, Jing. Ion-Specific Effects of Divalent Ions on the Structure of Polyelectrolyte Brushes. United States: N. p., 2019. Web. doi:10.1021/acs.langmuir.9b01984.
Copy to clipboard
Xu, Xin, Mastropietro, Dean, Ruths, Marina, Tirrell, Matthew, & Yu, Jing. Ion-Specific Effects of Divalent Ions on the Structure of Polyelectrolyte Brushes. United States. https://doi.org/10.1021/acs.langmuir.9b01984
Copy to clipboard
Xu, Xin, Mastropietro, Dean, Ruths, Marina, Tirrell, Matthew, and Yu, Jing. Thu . "Ion-Specific Effects of Divalent Ions on the Structure of Polyelectrolyte Brushes". United States. https://doi.org/10.1021/acs.langmuir.9b01984. https://www.osti.gov/servlets/purl/1580738.
Copy to clipboard
@article{osti_1580738,
title = {Ion-Specific Effects of Divalent Ions on the Structure of Polyelectrolyte Brushes},
author = {Xu, Xin and Mastropietro, Dean and Ruths, Marina and Tirrell, Matthew and Yu, Jing},
abstractNote = {Polyelectrolyte brushes consist of charged polymer chains attached on one end to a surface at high densities. They are relevant for many practical applications ranging from biosensors to drug delivery to colloidal stability. Their structure and functionality can be dramatically influenced by multivalent counterions in the solution environment. In this work, the surface forces apparatus (SFA) and atomic force microscopy (AFM) were used to investigate the effects of three alkaline earth divalent cations, Mg2+, Ca2+, and Ba2+, on the structures of polystyrenesulfonate (PSS) brushes tethered to mica and silicon oxide surfaces. While all these ions caused significant shrinkage of the height of the PSS brushes, strong ion-specific effects were observed. Mg2+ and C2+, caused homogeneous shrinkage; Ba2+ led to pinned-micelle like inhomogeneous structures. Isothermal titration calorimetry (ITC) demonstrated that this ion specificity was mainly caused by the difference in binding energy between sulfonate groups and the divalent cations. Considering the abundance of divalent cations in industrial processes, natural environments, and biological systems, the understanding of strong ion-specific effects of divalent counterions is of great importance for theoretical studies and various applications involving polyelectrolytes.},
doi = {10.1021/acs.langmuir.9b01984},
journal = {Langmuir},
number = 48,
volume = 35,
place = {United States},
year = {Thu Aug 15 00:00:00 EDT 2019},
month = {Thu Aug 15 00:00:00 EDT 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.langmuir.9b01984
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Effect of counterions on the swelling of spherical polyelectrolyte brushes
journal, February 2005

Larger cations can move faster in solid polymer electrolytes
journal, August 1990

Surface-Grafted Stimuli-Responsive Block Copolymer Brushes for the Thermo-, Photo- and pH-Sensitive Release of Dye Molecules
journal, September 2011

  • Kumar, Surjith; Dory, Yves L.; Lepage, Martin
  • Macromolecules, Vol. 44, Issue 18
  • DOI: 10.1021/ma2010102

Influence of Counterion Valency on the Conformational Behavior of Cylindrical Polyelectrolyte Brushes
journal, April 2009

  • Yan, Li-Tang; Xu, Youyong; Ballauff, Matthias
  • The Journal of Physical Chemistry B, Vol. 113, Issue 15
  • DOI: 10.1021/jp810648z

Principles Governing Mg, Ca, and Zn Binding and Selectivity in Proteins
journal, March 2003

  • Dudev, Todor; Lim, Carmay
  • Chemical Reviews, Vol. 103, Issue 3
  • DOI: 10.1021/cr020467n

Reversible Adhesion with Polyelectrolyte Brushes Tailored via the Uptake and Release of Trivalent Lanthanum Ions
journal, April 2015

  • Farina, Robert; Laugel, Nicolas; Yu, Jing
  • The Journal of Physical Chemistry C, Vol. 119, Issue 26
  • DOI: 10.1021/acs.jpcc.5b02121

Stimuli-responsive polymers grafted to nanopores and other nano-curved surfaces: structure, chemical equilibrium and transport
journal, January 2012

  • Tagliazucchi, Mario; Szleifer, Igal
  • Soft Matter, Vol. 8, Issue 28
  • DOI: 10.1039/c2sm25777g

Supramolecular Structures in Aqueous Solutions of Rigid Polyelectrolytes with Monovalent and Divalent Counterions
journal, October 2006

  • Kroeger, Anja; Belack, Joerg; Larsen, Antje
  • Macromolecules, Vol. 39, Issue 20
  • DOI: 10.1021/ma061228v

A Combined Experimental and Theoretical Study of Divalent Metal Ion Selectivity and Function in Proteins:  Application to E. coli Ribonuclease H1
journal, August 2003

  • Babu, C. Satheesan; Dudev, Todor; Casareno, R.
  • Journal of the American Chemical Society, Vol. 125, Issue 31
  • DOI: 10.1021/ja034956w

Phase separation kinetics of polyelectrolyte solutions
journal, December 2007

  • Kanai, Sonoko; Muthukumar, M.
  • The Journal of Chemical Physics, Vol. 127, Issue 24
  • DOI: 10.1063/1.2806299

Lubrication by charged polymers
journal, September 2003

  • Raviv, Uri; Giasson, Suzanne; Kampf, Nir
  • Nature, Vol. 425, Issue 6954
  • DOI: 10.1038/nature01970

van't Hoff and Calorimetric Enthalpies from Isothermal Titration Calorimetry:  Are There Significant Discrepancies? †
journal, February 2001

  • Horn, James R.; Russell, Donald; Lewis, Edwin A.
  • Biochemistry, Vol. 40, Issue 6
  • DOI: 10.1021/bi002408e

Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes
journal, December 2017

Brushes of strong polyelectrolytes in mixed mono- and tri-valent ionic media at fixed total ionic strengths
journal, January 2013

  • Farina, Robert; Laugel, Nicolas; Pincus, Philip
  • Soft Matter, Vol. 9, Issue 44
  • DOI: 10.1039/c3sm51450a

Brush Effects on DNA Chips: Thermodynamics, Kinetics, and Design Guidelines
journal, August 2005

Calcium channel selectivity for divalent and monovalent cations. Voltage and concentration dependence of single channel current in ventricular heart cells.
journal, September 1986

  • Hess, P.; Lansman, J. B.; Tsien, R. W.
  • Journal of General Physiology, Vol. 88, Issue 3
  • DOI: 10.1085/jgp.88.3.293

Self-Assembling Amphiphiles for Construction of Protein Molecular Architecture
journal, January 1996

  • Yu, Ying-Ching; Berndt, Peter; Tirrell, Matthew
  • Journal of the American Chemical Society, Vol. 118, Issue 50
  • DOI: 10.1021/ja9627656

End-tethered charged chains at surfaces
journal, November 2000

  • Guenoun, Patrick; Argillier, Jean-François; Tirrell, Matthew
  • Comptes Rendus de l'Académie des Sciences - Series IV - Physics, Vol. 1, Issue 9
  • DOI: 10.1016/S1296-2147(00)01128-8

Multivalent counterions diminish the lubricity of polyelectrolyte brushes
journal, June 2018

Competition among Metal Ions for Protein Binding Sites: Determinants of Metal Ion Selectivity in Proteins
journal, September 2013

  • Dudev, Todor; Lim, Carmay
  • Chemical Reviews, Vol. 114, Issue 1
  • DOI: 10.1021/cr4004665

A Study of Polyelectrolyte Brushes Formed from Adsorption of Amphiphilic Diblock Copolymers Using the Surface Forces Apparatus
journal, December 2002

  • Balastre, Marc; Li, Feng; Schorr, Phillip
  • Macromolecules, Vol. 35, Issue 25
  • DOI: 10.1021/ma011875g

Determination of the Structure of Polyelectrolyte Brushes
journal, December 1999

  • Tran, Y.; Auroy, P.; Lee, L-T.
  • Macromolecules, Vol. 32, Issue 26
  • DOI: 10.1021/ma990443r

Structure of Polyelectrolyte Brushes in the Presence of Multivalent Counterions
journal, July 2016

Collapse of grafted polyelectrolyte layer
journal, May 1991

  • Borisov, O. V.; Birshtein, T. M.; Zhulina, E. B.
  • Journal de Physique II, Vol. 1, Issue 5
  • DOI: 10.1051/jp2:1991186

Phase behavior of polyelectrolyte solutions with salt
journal, January 2009

  • Lee, Chi-Lun; Muthukumar, Murugappan
  • The Journal of Chemical Physics, Vol. 130, Issue 2
  • DOI: 10.1063/1.3054140

Predicting hydration energies for multivalent ions
journal, September 2014

  • Andersson, Martin P.; Stipp, Susan L. S.
  • Journal of Computational Chemistry, Vol. 35, Issue 28
  • DOI: 10.1002/jcc.23733

Competitive counterion binding and dehydration of polyelectrolytes in aqueous solutions
journal, January 1991

Electrochemical DNA sensors
journal, October 2003

  • Drummond, T. Gregory; Hill, Michael G.; Barton, Jacqueline K.
  • Nature Biotechnology, Vol. 21, Issue 10
  • DOI: 10.1038/nbt873

Microsurface Potential Measurements: Repulsive Forces between Polyelectrolyte Brushes in the Presence of Multivalent Counterions
journal, October 2008

  • Schneider, Christian; Jusufi, Arben; Farina, Robert
  • Langmuir, Vol. 24, Issue 19
  • DOI: 10.1021/la802303z

Hydration of Cations: A Key to Understanding of Specific Cation Effects on Aggregation Behaviors of PEO-PPO-PEO Triblock Copolymers
journal, August 2013

  • Lutter, Jacob C.; Wu, Tsung-yu; Zhang, Yanjie
  • The Journal of Physical Chemistry B, Vol. 117, Issue 35
  • DOI: 10.1021/jp405709x

Interaction of Proteins with Polyelectrolytes: Comparison of Theory to Experiment
journal, August 2018

Poisson–Boltzmann Theory of pH-Sensitive (Annealing) Polyelectrolyte Brush
journal, September 2011

Wettability and Antifouling Behavior on the Surfaces of Superhydrophilic Polymer Brushes
journal, April 2012

  • Kobayashi, Motoyasu; Terayama, Yuki; Yamaguchi, Hiroki
  • Langmuir, Vol. 28, Issue 18
  • DOI: 10.1021/la301033h

CHEMISTRY: Repair or Replacement--A Joint Perspective
journal, January 2009

Emerging applications of stimuli-responsive polymer materials
journal, January 2010

  • Stuart, Martien A. Cohen; Huck, Wilhelm T. S.; Genzer, Jan
  • Nature Materials, Vol. 9, Issue 2, p. 101-113
  • DOI: 10.1038/nmat2614

Limiting Laws and Counterion Condensation in Polyelectrolyte Solutions I. Colligative Properties
journal, August 1969

  • Manning, Gerald S.
  • The Journal of Chemical Physics, Vol. 51, Issue 3
  • DOI: 10.1063/1.1672157

Colloid stabilization with grafted polyelectrolytes
journal, May 1991

van't Hoff and Calorimetric Enthalpies II:  Effects of Linked Equilibria †
journal, June 2002

  • Horn, James R.; Brandts, John F.; Murphy, Kenneth P.
  • Biochemistry, Vol. 41, Issue 23
  • DOI: 10.1021/bi025626b

Lubrication at Physiological Pressures by Polyzwitterionic Brushes
journal, March 2009

Manipulating cylindrical polyelectrolyte brushes on the nanoscale by counterions: collapse transition to helical structures
journal, January 2009

  • Xu, Youyong; Bolisetty, Sreenath; Drechsler, Markus
  • Soft Matter, Vol. 5, Issue 2
  • DOI: 10.1039/B812179F

DNA condensation
journal, June 1996

Mechanical and chemical properties of poly(styrene-isobutylene-styrene) block copolymers: Effect of sulfonation and counter ion substitution
journal, January 2014

  • Suleiman, David; Padovani, Agnes M.; Negrón, Arnaldo A.
  • Journal of Applied Polymer Science, Vol. 131, Issue 11
  • DOI: 10.1002/app.40344
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: