Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes
Abstract
Multivalent counterion-induced bridging interactions have been identified as the key mechanism of drastic collapse of the height of polyelectrolyte (PE) brushes. In this article, we employ all-atom molecular dynamics (MD) simulations to quantify the bridging interactions in PE brushes for counterions of different sizes and valences. We identify that unlike the current notion, bridging interactions are not the sole function of the counterion valence. Rather the bridging interactions depend on the fraction of counterions (of a given type) that get physically condensed on the PE backbone as well as the size of the counterion solvation shell. These mechanisms ensure that certain monovalent counterions demonstrate much stronger bridging interactions than that witnessed for certain divalent and trivalent counterions, while certain counterions of identical valences show drastically different bridging. Here, we argue that these counterion-specific bridging interactions eventually enable not only the significant reduction of the PE brush height in presence of certain multivalent screening counterions, but may also give rise to scenarios where the brush height reduction for certain monovalent counterions is larger than certain divalent and trivalent counterions. This latter observation contradicts the experimental findings where the multivalent counterions invariably led to a larger decrease in the height of themore »
- Authors:
-
- Univ. of Maryland, College Park, MD (United States)
- Publication Date:
- Research Org.:
- Univ. of Maryland, College Park, MD (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1779578
- Grant/Contract Number:
- SC0017741
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 9; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 42 ENGINEERING; Counterions; Monomers; Layers; Solvation; Ions
Citation Formats
Pial, Turash Haque, Sachar, Harnoor Singh, and Das, Siddhartha. Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes. United States: N. p., 2021.
Web. doi:10.1021/acs.macromol.1c00328.
Pial, Turash Haque, Sachar, Harnoor Singh, & Das, Siddhartha. Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes. United States. https://doi.org/10.1021/acs.macromol.1c00328
Pial, Turash Haque, Sachar, Harnoor Singh, and Das, Siddhartha. Thu .
"Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes". United States. https://doi.org/10.1021/acs.macromol.1c00328. https://www.osti.gov/servlets/purl/1779578.
@article{osti_1779578,
title = {Quantification of Mono- and Multivalent Counterion-Mediated Bridging in Polyelectrolyte Brushes},
author = {Pial, Turash Haque and Sachar, Harnoor Singh and Das, Siddhartha},
abstractNote = {Multivalent counterion-induced bridging interactions have been identified as the key mechanism of drastic collapse of the height of polyelectrolyte (PE) brushes. In this article, we employ all-atom molecular dynamics (MD) simulations to quantify the bridging interactions in PE brushes for counterions of different sizes and valences. We identify that unlike the current notion, bridging interactions are not the sole function of the counterion valence. Rather the bridging interactions depend on the fraction of counterions (of a given type) that get physically condensed on the PE backbone as well as the size of the counterion solvation shell. These mechanisms ensure that certain monovalent counterions demonstrate much stronger bridging interactions than that witnessed for certain divalent and trivalent counterions, while certain counterions of identical valences show drastically different bridging. Here, we argue that these counterion-specific bridging interactions eventually enable not only the significant reduction of the PE brush height in presence of certain multivalent screening counterions, but may also give rise to scenarios where the brush height reduction for certain monovalent counterions is larger than certain divalent and trivalent counterions. This latter observation contradicts the experimental findings where the multivalent counterions invariably led to a larger decrease in the height of the PE brushes: we argue that this discrepancy stems from the fact that in our simulations we only consider densely grafted and short (and hence less flexible) PE brushes that hinder the formation of different laterally inhomogeneous structures (like pinned micelles and cylindrical bundles) that would have led to a larger brush height reduction (in experiments, which invariably consider longer and less densely grafted brushes, the formation of such inhomogeneous structures are primarily responsible for larger brush height reduction in presence of multivalent counterions). Finally, we also probe the dynamic properties of the counterions (i.e., their time-dependent displacements) and their bridging interactions (i.e., lifetime of bridging interactions).},
doi = {10.1021/acs.macromol.1c00328},
journal = {Macromolecules},
number = 9,
volume = 54,
place = {United States},
year = {Thu Apr 29 00:00:00 EDT 2021},
month = {Thu Apr 29 00:00:00 EDT 2021}
}
Works referenced in this record:
Recent developments in the co-delivery of siRNA and small molecule anticancer drugs for cancer treatment
journal, July 2014
- Saraswathy, Manju; Gong, Shaoqin
- Materials Today, Vol. 17, Issue 6
Contraction and Coagulation of Spherical Polyelectrolyte Brushes in the Presence of Ag + , Mg 2+ , and Ca 2+ Cations
journal, September 2016
- Ezhova, Anna; Huber, Klaus
- Macromolecules, Vol. 49, Issue 19
Spherical polyelectrolyte brushes in the presence of multivalent counterions: The effect of fluctuations and correlations as determined by molecular dynamics simulations
journal, March 2008
- Mei, Yu; Hoffmann, Martin; Ballauff, Matthias
- Physical Review E, Vol. 77, Issue 3
Molecular dynamics simulations of polyelectrolyte brushes under poor solvent conditions: Origins of bundle formation
journal, March 2014
- He, Gui-Li; Merlitz, Holger; Sommer, Jens-Uwe
- The Journal of Chemical Physics, Vol. 140, Issue 10
Morphologies of Planar Polyelectrolyte Brushes in a Poor Solvent: Molecular Dynamics Simulations and Scaling Analysis
journal, November 2009
- Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
- Langmuir, Vol. 25, Issue 22
Solvation Structure and Ion Complexation of La 3+ in a 1 Molal Aqueous Solution of Lanthanum Chloride
journal, June 2011
- Díaz-Moreno, Sofia; Ramos, Silvia; Bowron, Daniel T.
- The Journal of Physical Chemistry A, Vol. 115, Issue 24
Competitive calcium ion binding to end-tethered weak polyelectrolytes
journal, January 2018
- Nap, Rikkert J.; Park, Sung Hyun; Szleifer, Igal
- Soft Matter, Vol. 14, Issue 12
Overscreening, Co-Ion-Dominated Electroosmosis, and Electric Field Strength Mediated Flow Reversal in Polyelectrolyte Brush Functionalized Nanochannels
journal, April 2021
- Pial, Turash Haque; Sachar, Harnoor Singh; Desai, Parth Rakesh
- ACS Nano, Vol. 15, Issue 4
Cation Bridging Studied by Specular Neutron Reflection
journal, April 2013
- Wang, Xiaofan; Lee, Seung Yeon; Miller, Kathryn
- Langmuir, Vol. 29, Issue 18
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
Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes
journal, March 1977
- Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C.
- Journal of Computational Physics, Vol. 23, Issue 3
Steric Effects Control the Structure of the Solvated Lanthanum(III) Ion in Aqueous, Dimethyl Sulfoxide, and N , N ‘-Dimethylpropyleneurea Solution. An EXAFS and Large-Angle X-ray Scattering Study
journal, August 2000
- Näslund, Jan; Lindqvist-Reis, Patric; Persson, Ingmar
- Inorganic Chemistry, Vol. 39, Issue 18
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes
journal, December 2017
- Yu, Jing; Jackson, Nicholas E.; Xu, Xin
- Science Advances, Vol. 3, Issue 12
Ion-Specific Effects of Divalent Ions on the Structure of Polyelectrolyte Brushes
journal, August 2019
- Xu, Xin; Mastropietro, Dean; Ruths, Marina
- Langmuir, Vol. 35, Issue 48
Effect of pH and Molecular Length on the Structure and Dynamics of Short Poly(acrylic acid) in Dilute Solution: Detailed Molecular Dynamics Study
journal, April 2019
- Mintis, Dimitris G.; Mavrantzas, Vlasis G.
- The Journal of Physical Chemistry B, Vol. 123, Issue 19
Potassium, Calcium, and Magnesium Bridging of AOT to Mica at Constant Ionic Strength
journal, April 2019
- Allen, Finian J.; Truscott, Chris L.; Gutfreund, Philipp
- Langmuir, Vol. 35, Issue 17
Molecular-dynamics study of a three-dimensional one-component model for distortive phase transitions
journal, February 1978
- Schneider, T.; Stoll, E.
- Physical Review B, Vol. 17, Issue 3
Multivalent counterions diminish the lubricity of polyelectrolyte brushes
journal, June 2018
- Yu, J.; Jackson, N. E.; Xu, X.
- Science, Vol. 360, Issue 6396
Molecular Dynamics Analysis of Charge Transport in Ionic-Liquid Electrolytes Containing Added Salt with Mono, Di, and Trivalent Metal Cations
journal, April 2018
- Vicent-Luna, José Manuel; Azaceta, Eneko; Hamad, Said
- ChemPhysChem, Vol. 19, Issue 13
Morphologies of spherical bidisperse polyelectrolyte brushes in the presence of trivalent counterions
journal, November 2020
- Li, Yan; Hao, Qing-Hai; Xia, Sheng-Yuan
- Chemical Physics, Vol. 539
A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984
- Nosé, Shuichi
- The Journal of Chemical Physics, Vol. 81, Issue 1
Layer-by-Layer Assembly of Polyelectrolytes into Ionic Current Rectifying Solid-State Nanopores: Insights from Theory and Experiment
journal, June 2010
- Ali, Mubarak; Yameen, Basit; Cervera, Javier
- Journal of the American Chemical Society, Vol. 132, Issue 24
Structure of Polyelectrolyte Brushes in the Presence of Multivalent Counterions
journal, July 2016
- Yu, Jing; Mao, Jun; Yuan, Guangcui
- Macromolecules, Vol. 49, Issue 15
Single Conical Nanopores Displaying pH-Tunable Rectifying Characteristics. Manipulating Ionic Transport With Zwitterionic Polymer Brushes
journal, February 2009
- Yameen, Basit; Ali, Mubarak; Neumann, Reinhard
- Journal of the American Chemical Society, Vol. 131, Issue 6
Structure of Polyelectrolyte Brushes on Polarizable Substrates
journal, April 2020
- Yuan, Jiaxing; Antila, Hanne S.; Luijten, Erik
- Macromolecules, Vol. 53, Issue 8
Hydration of the Yttrium(III) Ion in Aqueous Solution. An X-ray Diffraction and XAFS Structural Study
journal, December 1999
- Lindqvist-Reis, Patric; Lamble, Kathryn; Pattanaik, Sidhartha
- The Journal of Physical Chemistry B, Vol. 104, Issue 2
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996
- Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian
- Journal of the American Chemical Society, Vol. 118, Issue 45
Stimuli-Responsive Colloidal Systems from Mixed Brush-Coated Nanoparticles
journal, August 2007
- Motornov, M.; Sheparovych, Ro.; Lupitskyy, R.
- Advanced Functional Materials, Vol. 17, Issue 14
Molecular Dynamics Simulation of Ion Mobility. 2. Alkali Metal and Halide Ions Using the SPC/E Model for Water at 25 °C †
journal, January 1996
- Lee, Song Hi; Rasaiah, Jayendran C.
- The Journal of Physical Chemistry, Vol. 100, Issue 4
Simulating Monovalent and Divalent Ions in Aqueous Solution Using a Drude Polarizable Force Field
journal, January 2010
- Yu, Haibo; Whitfield, Troy W.; Harder, Edward
- Journal of Chemical Theory and Computation, Vol. 6, Issue 3
Hollow silica–polyelectrolyte composite nanoparticles for controlled drug delivery
journal, October 2018
- Yang, Qingsong; Li, Li; Zhao, Fang
- Journal of Materials Science, Vol. 54, Issue 3
Rational Design of Particle Mesh Ewald Compatible Lennard-Jones Parameters for +2 Metal Cations in Explicit Solvent
journal, May 2013
- Li, Pengfei; Roberts, Benjamin P.; Chakravorty, Dhruva K.
- Journal of Chemical Theory and Computation, Vol. 9, Issue 6
An Anionic Surfactant on an Anionic Substrate: Monovalent Cation Binding
journal, August 2017
- Allen, Finian J.; Griffin, Lucy R.; Alloway, Richard M.
- Langmuir, Vol. 33, Issue 32
Towards accurate solvation dynamics of divalent cations in water using the polarizable amoeba force field: From energetics to structure
journal, August 2006
- Piquemal, Jean-Philip; Perera, Lalith; Cisneros, G. Andrés
- The Journal of Chemical Physics, Vol. 125, Issue 5
Comparing Solvophobic and Multivalent Induced Collapse in Polyelectrolyte Brushes
journal, January 2017
- Jackson, Nicholas E.; Brettmann, Blair K.; Vishwanath, Venkatram
- ACS Macro Letters, Vol. 6, Issue 2
Effect of counterion excluded volume on the conformational behavior of polyelectrolyte chains
journal, January 2018
- Gordievskaya, Yulia D.; Gavrilov, Alexey A.; Kramarenko, Elena Yu.
- Soft Matter, Vol. 14, Issue 8
Collapse of Spherical Polyelectrolyte Brushes in the Presence of Multivalent Counterions
journal, October 2006
- Mei, Yu; Lauterbach, Karlheinz; Hoffmann, Martin
- Physical Review Letters, Vol. 97, Issue 15
Polymer-coated nanoparticles for enhanced oil recovery
journal, March 2014
- ShamsiJazeyi, Hadi; Miller, Clarence A.; Wong, Michael S.
- Journal of Applied Polymer Science, Vol. 131, Issue 15
Visualization and analysis of atomistic simulation data with OVITO–the Open Visualization Tool
journal, December 2009
- Stukowski, Alexander
- Modelling and Simulation in Materials Science and Engineering, Vol. 18, Issue 1
Heterogeneous Morphology and Dynamics of Polyelectrolyte Brush Condensates in Trivalent Counterion Solution
journal, February 2017
- Liu, Lei; Pincus, Philip A.; Hyeon, Changbong
- Macromolecules, Vol. 50, Issue 4
Lateral Structure Formation in Polyelectrolyte Brushes Induced by Multivalent Ions
journal, January 2017
- Brettmann, Blair; Pincus, Philip; Tirrell, Matthew
- Macromolecules, Vol. 50, Issue 3
Densely Grafted Polyelectrolyte Brushes Trigger “Water-in-Salt”-like Scenarios and Ultraconfinement Effect
journal, June 2020
- Sachar, Harnoor Singh; Pial, Turash Haque; Desai, Parth Rakesh
- Matter, Vol. 2, Issue 6
Scaling behavior of polyelectrolytes and polyampholytes: Simulation by an ensemble growth method
journal, September 1991
- Higgs, P. G.; Orland, H.
- The Journal of Chemical Physics, Vol. 95, Issue 6
Effect of Counterion Size on the Structure of a Flexible Polyelectrolyte Chain in Low-Polar Solvents
journal, November 2018
- Gordievskaya, Yu. D.; Kramarenko, E. Yu.
- Polymer Science, Series C, Vol. 60, Issue S1
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
Polyelectrolyte brushes: theory, modelling, synthesis and applications
journal, January 2015
- Das, Siddhartha; Banik, Meneka; Chen, Guang
- Soft Matter, Vol. 11, Issue 44
Structural parameters of close surroundings of Sr2+ and Ba2+ ions in aqueous solutions of their salts
journal, February 2011
- Smirnov, P. R.; Trostin, V. N.
- Russian Journal of General Chemistry, Vol. 81, Issue 2
Influence of Ion Solvation on the Properties of Electrolyte Solutions
journal, April 2018
- Andreev, Marat; de Pablo, Juan J.; Chremos, Alexandros
- The Journal of Physical Chemistry B, Vol. 122, Issue 14
Determination of Alkali and Halide Monovalent Ion Parameters for Use in Explicitly Solvated Biomolecular Simulations
journal, July 2008
- Joung, In Suk; Cheatham, Thomas E.
- The Journal of Physical Chemistry B, Vol. 112, Issue 30
Microstructure, dynamics and optical properties of metal-doped imidazolium-based ionic liquids
journal, November 2020
- Rodríguez-Fernández, Carlos Damián; Montes-Campos, Hadrián; López-Lago, Elena
- Journal of Molecular Liquids, Vol. 317
Parameterization of Highly Charged Metal Ions Using the 12-6-4 LJ-Type Nonbonded Model in Explicit Water
journal, August 2014
- Li, Pengfei; Song, Lin Frank; Merz, Kenneth M.
- The Journal of Physical Chemistry B, Vol. 119, Issue 3
The missing term in effective pair potentials
journal, November 1987
- Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P.
- The Journal of Physical Chemistry, Vol. 91, Issue 24