Charge regulation and local dielectric function in planar polyelectrolyte brushes

Kumar, Rajeev; Sumpter, Bobby G.; Kilbey, II, S Michael

doi:10.1063/1.4729158

Charge regulation and local dielectric function in planar polyelectrolyte brushes

Journal Article · Fri Jun 01 00:00:00 EDT 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4729158· OSTI ID:1043323

^[1]; ^[1]; Kilbey, II, S Michael ^[1]

ORNL

Understanding the effect of inhomogeneity on the charge regulation and dielectric properties, andhow it depends on the conformational characteristics of the macromolecules is a long-standing problem. In order to address this problem, we have developed a field-theory to study charge regulation and local dielectric function in planar polyelectrolyte brushes. The theory is used to study a polyacid brush, which is comprised of chains end-grafted at the solid-fluid interface, in equilibrium with a bulk solution containing monovalent salt ions, solvent molecules, and pH controlling acid. In particular, we focus on the effects of the concentration of added salt and pH of the bulk in determining the local charge and dielectric function. Our theoretical investigations reveal that the dipole moment of the ion-pairs formed as a result of counterion adsorption on the chain backbones play a key rolein affecting the local dielectric function. For polyelectrolytes made of monomers having dipole moments lower than the solvent molecules, dielectric decrement is predicted inside the brush region.However, the formation of ion-pairs (due to adsorption of counterions coming from the dissociationof added salt) more polar than the solvent molecules is shown to increase the magnitude of the dielectric function with respect to its bulk value. Furthermore, an increase in the bulk salt concentration is shown to increase the local charge inside the brush region.

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: DOE Office of Science; USDOE

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1043323

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 136; ISSN JCPSA6; ISSN 0021-9606

Country of Publication:: United States

Language:: English

References (57)

Spherical polyelectrolyte brushes Ballauff, M. Progress in Polymer Science, Vol. 32, Issue 10 https://doi.org/10.1016/j.progpolymsci.2007.05.002	journal	October 2007
Entropic Elasticity of Single Polymer Chains of Poly(methacrylic acid) Measured by Atomic Force Microscopy Ortiz, C.; Hadziioannou, G. Macromolecules, Vol. 32, Issue 3 https://doi.org/10.1021/ma981245n	journal	February 1999
Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates: 1. Experiment Wu, Tao; Gong, Peng; Szleifer, Igal Macromolecules, Vol. 40, Issue 24, p. 8756-8764 https://doi.org/10.1021/ma0710176	journal	November 2007
Phase Behavior and Charge Regulation of Weak Polyelectrolyte Grafted Layers Gong, Peng; Genzer, Jan; Szleifer, I. Physical Review Letters, Vol. 98, Issue 1 https://doi.org/10.1103/PhysRevLett.98.018302	journal	January 2007
Nonlinear response effects in continuum models of the hydration of ions Sandberg, Lars; Edholm, Olle The Journal of Chemical Physics, Vol. 116, Issue 7 https://doi.org/10.1063/1.1435566	journal	February 2002
Adsorption of chain molecules with a polar head a scaling description Alexander, S. Journal de Physique, Vol. 38, Issue 8 https://doi.org/10.1051/jphys:01977003808098300	journal	January 1977
Dielectric properties and conductivity of styrene-methacrylic acid copolymers and partially neutralized salts Arai, K.; Eisenberg, A. Journal of Macromolecular Science, Part B, Vol. 17, Issue 4 https://doi.org/10.1080/00222348008212838	journal	May 1980
Weak polyelectrolytes tethered to surfaces: Effect of geometry, acid–base equilibrium and electrical permittivity Nap, Rikkert; Gong, Peng; Szleifer, Igal Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 18 https://doi.org/10.1002/polb.20896	journal	January 2006
Limiting Laws and Counterion Condensation in Polyelectrolyte Solutions I. Colligative Properties Manning, Gerald S. The Journal of Chemical Physics, Vol. 51, Issue 3 https://doi.org/10.1063/1.1672157	journal	August 1969
Direct polymerization of surface-tethered polyelectrolyte layers in aqueous solution via surface-confined atom transfer radical polymerization Sankhe, Amit Y.; Husson, Scott M.; Kilbey, S. Michael Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 4 https://doi.org/10.1002/pola.21817	journal	January 2007
Electric Moments of Molecules in Liquids Onsager, Lars Journal of the American Chemical Society, Vol. 58, Issue 8 https://doi.org/10.1021/ja01299a050	journal	August 1936
Computation of multiphase systems with phase field models Badalassi, V. E.; Ceniceros, H. D.; Banerjee, S. Journal of Computational Physics, Vol. 190, Issue 2 https://doi.org/10.1016/S0021-9991(03)00280-8	journal	September 2003
The Dielectric Constant of Water and the Saturation Effect Booth, F. The Journal of Chemical Physics, Vol. 19, Issue 4 https://doi.org/10.1063/1.1748233	journal	April 1951
Theory of Ionizable Polymer Brushes Zhulina, E. B.; Birshtein, T. M.; Borisov, O. V. Macromolecules, Vol. 28, Issue 5 https://doi.org/10.1021/ma00109a021	journal	September 1995
Dielectric Properties of Polyelectrolyte Solutions Mandel, M.; Odijk, T. Annual Review of Physical Chemistry, Vol. 35, Issue 1 https://doi.org/10.1146/annurev.pc.35.100184.000451	journal	October 1984
Effect of the finite extensibility of polymer chains and of the finite size of added electrolyte ions on polyelectrolyte brushes Misra, Sanjay; Varanasi, Sasidhar The Journal of Chemical Physics, Vol. 95, Issue 3 https://doi.org/10.1063/1.460966	journal	August 1991
Fluctuation in electrolyte solutions: The self energy Wang, Zhen-Gang Physical Review E, Vol. 81, Issue 2 https://doi.org/10.1103/PhysRevE.81.021501	journal	February 2010
Solvation effect on conformations of 1,2:dimethoxyethane: Charge-dependent nonlinear response in implicit solvent models Jha, Abhishek K.; Freed, Karl F. The Journal of Chemical Physics, Vol. 128, Issue 3 https://doi.org/10.1063/1.2815764	journal	January 2008
Multilamellar Structures Induced by Hydrophilic and Hydrophobic Ions Added to a Binary Mixture of D 2 O and 3-Methylpyridine Sadakane, Koichiro; Onuki, Akira; Nishida, Koji Physical Review Letters, Vol. 103, Issue 16 https://doi.org/10.1103/PhysRevLett.103.167803	journal	October 2009
Counterion Adsorption on Flexible Polyelectrolytes: Comparison of Theories Kumar, Rajeev; Kundagrami, Arindam; Muthukumar, M. Macromolecules, Vol. 42, Issue 4 https://doi.org/10.1021/ma801799e	journal	February 2009
Ionizable polyelectrolyte brushes: brush height and electrosteric interaction Biesheuvel, P. Maarten Journal of Colloid and Interface Science, Vol. 275, Issue 1 https://doi.org/10.1016/j.jcis.2004.02.024	journal	July 2004
Langevin-Debye Model for Nonlinear Electrostatic Screening of Solvated Ions Gong, Haipeng; Freed, Karl F. Physical Review Letters, Vol. 102, Issue 5 https://doi.org/10.1103/PhysRevLett.102.057603	journal	February 2009
Polymer Brushes Milner, S. T. Science, Vol. 251, Issue 4996 https://doi.org/10.1126/science.251.4996.905	journal	February 1991
Conformations of Polymers Attached to an Interface de Gennes, P. G. Macromolecules, Vol. 13, Issue 5 https://doi.org/10.1021/ma60077a009	journal	September 1980
Dielectric behaviour of aqueous polyelectrolyte solutions. Part 1 Mandel, M.; Jenard, A. Transactions of the Faraday Society, Vol. 59 https://doi.org/10.1039/tf9635902158	journal	January 1963
Mesoscopic structure in near-critical mixtures of D ₂ O and 3-methylpyridine with salts Sadakane, Koichiro; Seto, Hideki; Endo, Hitoshi Journal of Applied Crystallography, Vol. 40, Issue s1 https://doi.org/10.1107/S0021889806055658	journal	January 2007
Charge-density and order-parameter waves in liquid and solid electrolytes in the vicinity of the critical point Nabutovskii, V. M.; Nemov, N. A.; Peisakhovich, Yu. G. Physics Letters A, Vol. 79, Issue 1 https://doi.org/10.1016/0375-9601(80)90329-1	journal	September 1980
Analytical Self-Consistent-Field Model of Weak Polyacid Brushes Lyatskaya, Yu. V.; Leermakers, F. A. M.; Fleer, G. J. Macromolecules, Vol. 28, Issue 10 https://doi.org/10.1021/ma00114a009	journal	May 1995
Contributions from Dispersion and Born Self-Free Energies to the Solvation Energies of Salt Solutions Boström, M.; Ninham, B. W. The Journal of Physical Chemistry B, Vol. 108, Issue 33 https://doi.org/10.1021/jp048517a	journal	August 2004
Implicit-Explicit Methods for Time-Dependent Partial Differential Equations Ascher, Uri M.; Ruuth, Steven J.; Wetton, Brian T. R. SIAM Journal on Numerical Analysis, Vol. 32, Issue 3 https://doi.org/10.1137/0732037	journal	June 1995
Ultrasoft primitive model of polyionic solutions: Structure, aggregation, and dynamics Coslovich, Daniele; Hansen, Jean-Pierre; Kahl, Gerhard The Journal of Chemical Physics, Vol. 134, Issue 24 https://doi.org/10.1063/1.3602469	journal	June 2011
A Periodic Structure in a Mixture of D ₂ O/3-Methylpyridine/NaBPh ₄ Induced by Solvation Effect Sadakane, Koichiro; Seto, Hideki; Endo, Hitoshi Journal of the Physical Society of Japan, Vol. 76, Issue 11 https://doi.org/10.1143/JPSJ.76.113602	journal	November 2007
Self-Consistent Field Theory Study of the Effect of Grafting Density on the Height of a Weak Polyelectrolyte Brush Witte, Kevin N.; Kim, Sangtae; Won, You-Yeon The Journal of Physical Chemistry B, Vol. 113, Issue 32 https://doi.org/10.1021/jp809814j	journal	August 2009
Correlation functions for the electrolyte near the critical point of pure solvent Nabutovskii, V. M.; Nemov, N. A.; Peisakhovich, Yu. G. Molecular Physics, Vol. 54, Issue 4 https://doi.org/10.1080/00268978500103311	journal	March 1985
Dielectric behaviour of aqueous polyelectrolyte solutions. Part 2 Mandel, M.; Jenard, A. Transactions of the Faraday Society, Vol. 59 https://doi.org/10.1039/tf9635902170	journal	January 1963
Swelling Behavior of Multiresponsive Poly(methacrylic acid)- block- -poly( N- isopropylacrylamide) Brushes Synthesized Using Surface-Initiated Photoiniferter-Mediated Photopolymerization : Multiresponsive Polymer Brushes Rahane, Santosh B.; Floyd, J. Alaina; Metters, Andrew T. Advanced Functional Materials, Vol. 18, Issue 8 https://doi.org/10.1002/adfm.200701411	journal	April 2008
Dielectric properties of polyelectrolytes. II. A theory of dielectric increment due to ion fluctuation by a matrix method Minakata, Akira; Imai, Nobuhisa; Oosawa, Fumio Biopolymers, Vol. 11, Issue 2 https://doi.org/10.1002/bip.1972.360110204	journal	February 1972
Charge on a weak polyelectrolyte Wang, Shengqin; Granick, Steve; Zhao, Jiang The Journal of Chemical Physics, Vol. 129, Issue 24 https://doi.org/10.1063/1.3055596	journal	December 2008
Counterion structure and dynamics in polyelectrolyte solutions Prabhu, Vivek M. Current Opinion in Colloid & Interface Science, Vol. 10, Issue 1-2 https://doi.org/10.1016/j.cocis.2005.04.002	journal	August 2005
Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates 2. Theory Gong, Peng; Wu, Tao; Genzer, Jan Macromolecules, Vol. 40, Issue 24, p. 8765-8773 https://doi.org/10.1021/ma071018y	journal	November 2007
Potentiometric titration of polyacrylic and polymethacrylic acids with alkali metal and quaternary ammonium bases Gregor, Harry P.; Frederick, Michael Journal of Polymer Science, Vol. 23, Issue 103 https://doi.org/10.1002/pol.1957.1202310338	journal	January 1957
Solvation effects in near-critical binary mixtures Onuki, Akira; Kitamura, Hikaru The Journal of Chemical Physics, Vol. 121, Issue 7 https://doi.org/10.1063/1.1769357	journal	August 2004
Phase diagram of a mixed polymer brush Müller, M. Physical Review E, Vol. 65, Issue 3 https://doi.org/10.1103/PhysRevE.65.030802	journal	February 2002
Dielectric spectroscopy and conductivity of polyelectrolyte solutions Bordi, F.; Cametti, C.; Colby, R. H. Journal of Physics: Condensed Matter, Vol. 16, Issue 49 https://doi.org/10.1088/0953-8984/16/49/R01	journal	November 2004
Effects of Ion Solvation on the Miscibility of Binary Polymer Blends ^† Wang, Zhen-Gang The Journal of Physical Chemistry B, Vol. 112, Issue 50 https://doi.org/10.1021/jp806897t	journal	December 2008
A polyelectrolyte brush theory Misra, Sanjay; Varanasi, Sasidhar; Varanasi, P. P. Macromolecules, Vol. 22, Issue 11 https://doi.org/10.1021/ma00201a007	journal	November 1989
The polyelectrolyte brush: poor solvent Ross, R. S.; Pincus, P. Macromolecules, Vol. 25, Issue 8 https://doi.org/10.1021/ma00034a018	journal	April 1992
Ion Binding and Ion Specificity: The Hofmeister Effect and Onsager and Lifshitz Theories Ninham, Barry W.; Yaminsky, Vassili Langmuir, Vol. 13, Issue 7 https://doi.org/10.1021/la960974y	journal	April 1997
Electrostatic correlations: from plasma to biology Levin, Yan Reports on Progress in Physics, Vol. 65, Issue 11 https://doi.org/10.1088/0034-4885/65/11/201	journal	September 2002
Dielectric Constant of Polar Liquids at High Field Strengths Booth, F. The Journal of Chemical Physics, Vol. 23, Issue 3 https://doi.org/10.1063/1.1742009	journal	March 1955
Polyelectrolyte brushes Ballauff, Matthias; Borisov, Oleg Current Opinion in Colloid & Interface Science, Vol. 11, Issue 6 https://doi.org/10.1016/j.cocis.2006.12.002	journal	December 2006
Effects of the Salt Concentration on Charge Regulation in Tethered Polyacid Monolayers Uline, Mark J.; Rabin, Yitzhak; Szleifer, Igal Langmuir, Vol. 27, Issue 8 https://doi.org/10.1021/la104906r	journal	April 2011
Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions Tagliazucchi, M.; de la Cruz, M. O.; Szleifer, I. Proceedings of the National Academy of Sciences, Vol. 107, Issue 12 https://doi.org/10.1073/pnas.0913340107	journal	March 2010
Self-Consistent Field Study of Polyelectrolyte Brushes Seki, Hidetsugu; Y. Suzuki, Yasuo; Orland, Henri Journal of the Physical Society of Japan, Vol. 76, Issue 10 https://doi.org/10.1143/JPSJ.76.104601	journal	October 2007
The nonlinear dielectric behavior of water: Comparisons of various approaches to the nonlinear dielectric increment Fulton, Robert L. The Journal of Chemical Physics, Vol. 130, Issue 20 https://doi.org/10.1063/1.3139211	journal	May 2009
Investigation of the interfacial tension of complex coacervates using field-theoretic simulations Riggleman, Robert A.; Kumar, Rajeev; Fredrickson, Glenn H. The Journal of Chemical Physics, Vol. 136, Issue 2 https://doi.org/10.1063/1.3674305	journal	January 2012
Long-range periodic structure induced by coupling of the solvation effect and concentration fluctuation in water and 3-methylpyridine with salts Sadakane, K.; Seto, H.; Nagao, M. Chemical Physics Letters, Vol. 426, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.05.028	journal	July 2006

Similar Records

Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes

Journal Article · Sat Mar 05 23:00:00 EST 2016 · Journal of Polymer Science. Part B, Polymer Physics · OSTI ID:1240518

Electroresponse of weak polyelectrolyte brushes

Journal Article · Thu Sep 14 00:00:00 EDT 2023 · European Physical Journal. E, Soft Matter (print) · OSTI ID:2000194

Related Subjects

36 MATERIALS SCIENCE
ADSORPTION
DIELECTRIC MATERIALS
DIELECTRIC PROPERTIES
DIPOLE MOMENTS
DISSOCIATION
ELECTROLYTES
FIELD THEORIES
ION PAIRS
MONOMERS
SOLVENTS

Charge regulation and local dielectric function in planar polyelectrolyte brushes

Citation Formats

References (57)

Similar Records

Related Subjects