Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes
Abstract
Spatial dependencies of monomer volume fraction profiles of pH responsive polyelectrolyte brushes were investigated using field theories and neutron reflectivity experiments. In particular, planar polyelectrolyte brushes in good solvent were studied and direct comparisons between predictions of the theories and experimental measurements are presented. The comparisons between the theories and the experimental data reveal that solvent entropy and ion-pairs resulting from adsorption of counterions from the added salt play key roles in affecting the monomer distribution and must be taken into account in modeling polyelectrolyte brushes. Furthermore, the utility of this physics-based approach based on these theories for the prediction and interpretation of neutron reflectivity profiles in the context of pH responsive planar polyelectrolyte brushes such as polybasic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and polyacidic poly(methacrylic acid) (PMAA) brushes is demonstrated. The approach provides a quantitative way of estimating molecular weights of the polymers polymerized using surface-initiated atom transfer radical polymerization.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1240518
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Polymer Science. Part B, Polymer Physics
- Additional Journal Information:
- Journal Name: Journal of Polymer Science. Part B, Polymer Physics; Journal ID: ISSN 0887-6266
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Mahalik, Jyoti P., Yang, Yubo, Deodhar, Chaitra V., Ankner, John Francis, Lokitz, Bradley S., Kilbey, II, S. Michael, Sumpter, Bobby G., and Kumar, Rajeev. Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes. United States: N. p., 2016.
Web. doi:10.1002/polb.24008.
Mahalik, Jyoti P., Yang, Yubo, Deodhar, Chaitra V., Ankner, John Francis, Lokitz, Bradley S., Kilbey, II, S. Michael, Sumpter, Bobby G., & Kumar, Rajeev. Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes. United States. https://doi.org/10.1002/polb.24008
Mahalik, Jyoti P., Yang, Yubo, Deodhar, Chaitra V., Ankner, John Francis, Lokitz, Bradley S., Kilbey, II, S. Michael, Sumpter, Bobby G., and Kumar, Rajeev. Sun .
"Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes". United States. https://doi.org/10.1002/polb.24008. https://www.osti.gov/servlets/purl/1240518.
@article{osti_1240518,
title = {Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes},
author = {Mahalik, Jyoti P. and Yang, Yubo and Deodhar, Chaitra V. and Ankner, John Francis and Lokitz, Bradley S. and Kilbey, II, S. Michael and Sumpter, Bobby G. and Kumar, Rajeev},
abstractNote = {Spatial dependencies of monomer volume fraction profiles of pH responsive polyelectrolyte brushes were investigated using field theories and neutron reflectivity experiments. In particular, planar polyelectrolyte brushes in good solvent were studied and direct comparisons between predictions of the theories and experimental measurements are presented. The comparisons between the theories and the experimental data reveal that solvent entropy and ion-pairs resulting from adsorption of counterions from the added salt play key roles in affecting the monomer distribution and must be taken into account in modeling polyelectrolyte brushes. Furthermore, the utility of this physics-based approach based on these theories for the prediction and interpretation of neutron reflectivity profiles in the context of pH responsive planar polyelectrolyte brushes such as polybasic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and polyacidic poly(methacrylic acid) (PMAA) brushes is demonstrated. The approach provides a quantitative way of estimating molecular weights of the polymers polymerized using surface-initiated atom transfer radical polymerization.},
doi = {10.1002/polb.24008},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = ,
volume = ,
place = {United States},
year = {Sun Mar 06 00:00:00 EST 2016},
month = {Sun Mar 06 00:00:00 EST 2016}
}
Web of Science
Works referenced in this record:
Role of Ionic Strength on the Relationship of Biopolymer Conformation, DLVO Contributions, and Steric Interactions to Bioadhesion of P seudomonas p utida KT2442
journal, July 2003
- Abu-Lail, Nehal I.; Camesano, Terri A.
- Biomacromolecules, Vol. 4, Issue 4
The effect of solvent polarity on the molecular surface properties and adhesion of Escherichia coli
journal, August 2006
- Abu-Lail, Nehal I.; Camesano, Terri A.
- Colloids and Surfaces B: Biointerfaces, Vol. 51, Issue 1
Lubrication at Physiological Pressures by Polyzwitterionic Brushes
journal, March 2009
- Chen, M.; Briscoe, W. H.; Armes, S. P.
- Science, Vol. 323, Issue 5922
κ-casein as a polyelectrolyte brush on the surface of casein micelles
journal, October 1996
- de Kruif, C. G.; Zhulina, Ekatherina B.
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 117, Issue 1-2
Adhesion and Stable Low Friction Provided by a Subnanometer-Thick Monolayer of a Natural Polysaccharide †
journal, February 2008
- Gourdon, Delphine; Lin, Qi; Oroudjev, Emin
- Langmuir, Vol. 24, Issue 4
Molecular mechanisms of synovial joint lubrication
journal, August 2006
- Klein, J.
- Proceedings of the Institution of Mechanical Engineers, Part J: Journal of Engineering Tribology, Vol. 220, Issue 8
Polymers in living systems: from biological lubrication to tissue engineering and biomedical devices: POLYMERS: FROM BIOLOGICAL LUBRICATION TO TISSUE ENGINEERING
journal, March 2012
- Klein, Jacob
- Polymers for Advanced Technologies, Vol. 23, Issue 4
How the projection domains of NF-L and α-internexin determine the conformations of NF-M and NF-H in neurofilaments
journal, March 2010
- Leermakers, F. A. M.; Zhulina, E. B.
- European Biophysics Journal, Vol. 39, Issue 9
Lubrication by charged polymers
journal, September 2003
- Raviv, Uri; Giasson, Suzanne; Kampf, Nir
- Nature, Vol. 425, Issue 6954
Normal and Shear Interactions between Hyaluronan–Aggrecan Complexes Mimicking Possible Boundary Lubricants in Articular Cartilage in Synovial Joints
journal, September 2012
- Seror, Jasmine; Merkher, Yulia; Kampf, Nir
- Biomacromolecules, Vol. 13, Issue 11
Prediction of the viscoelastic properties of the equivalent particle for the intercalated multi-layer stack of nanoplastics
journal, December 2007
- Zhang, Weimin; Zhang, Ping; Deng, Xuhui
- Acta Mechanica Solida Sinica, Vol. 20, Issue 4
Effect of the Ionic Strength and pH on the Equilibrium Structure of a Neurofilament Brush
journal, September 2007
- Zhulina, E. B.; Leermakers, F. A. M.
- Biophysical Journal, Vol. 93, Issue 5
Polymer Brushes: Routes toward Mechanosensitive Surfaces
journal, March 2010
- Bünsow, Johanna; Kelby, Tim S.; Huck, Wilhelm T. S.
- Accounts of Chemical Research, Vol. 43, Issue 3
Glucose-responsive polymer brushes for microcantilever sensing
journal, January 2010
- Chen, Tao; Chang, Debby P.; Liu, Ting
- Journal of Materials Chemistry, Vol. 20, Issue 17
Smart polymer brushes and their emerging applications
journal, January 2012
- Peng, Shunjin; Bhushan, Bharat
- RSC Advances, Vol. 2, Issue 23
Water Soluble Responsive Polymer Brushes
journal, December 2011
- Weir, Michael P.; Parnell, Andrew J.
- Polymers, Vol. 3, Issue 4
Scaling Theory of Strongly Charged Cylindrical Polyelectrolyte Brushes
journal, June 2012
- Qu, Li-Jian
- Communications in Theoretical Physics, Vol. 57, Issue 6
Polyelectrolyte brushes in monovalent and multivalent salt solutions
journal, June 2014
- Guptha, Vijeth Sathyanarayana; Hsiao, Pai-Yi
- Polymer, Vol. 55, Issue 12
Strongly Charged Polyelectrolyte Brushes: A Molecular Dynamics Study
journal, April 2000
- Csajka, Félix S.; Seidel, Christian
- Macromolecules, Vol. 33, Issue 7
Collapse of polyelectrolyte brushes: Scaling theory and simulations
journal, April 2001
- Csajka, F. S.; Netz, R. R.; Seidel, C.
- The European Physical Journal E, Vol. 4, Issue 4
Nonlinear Osmotic Brush Regime: Experiments, Simulations and Scaling Theory
journal, October 2004
- Ahrens, Heiko; Förster, Stephan; Helm, Christiane A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 43
Synthesis and swelling behavior of a weak polyacid brush
journal, September 2002
- Biesalski, M.; Johannsmann, D.; Rühe, J.
- The Journal of Chemical Physics, Vol. 117, Issue 10
Polyelectrolytes tethered to a similarly charged surface
journal, May 2001
- Borisov, O. V.; Leermakers, F. A. M.; Fleer, G. J.
- The Journal of Chemical Physics, Vol. 114, Issue 17
Annealing polyelectrolytes at charged interfaces
journal, November 2003
- Borisov, O. V.; Boulakh, A. B.; Zhulina, E. B.
- The European Physical Journal E, Vol. 12, Issue 4
Ionizable polyelectrolyte brushes: brush height and electrosteric interaction
journal, July 2004
- Biesheuvel, P. Maarten
- Journal of Colloid and Interface Science, Vol. 275, Issue 1
Analytical Self-Consistent-Field Model of Weak Polyacid Brushes
journal, May 1995
- Lyatskaya, Yu. V.; Leermakers, F. A. M.; Fleer, G. J.
- Macromolecules, Vol. 28, Issue 10
Screening Effects in a Polyelectrolyte Brush: Self-Consistent-Field Theory
journal, June 2000
- Zhulina, E. B.; Klein Wolterink, J.; Borisov, O. V.
- Macromolecules, Vol. 33, Issue 13
Poisson–Boltzmann Theory of pH-Sensitive (Annealing) Polyelectrolyte Brush
journal, September 2011
- Zhulina, E. B.; Borisov, O. V.
- Langmuir, Vol. 27, Issue 17
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
Polyelectrolyte Brushes: MD Simulation and SCF Theory
journal, September 2010
- He, Su-zhen; Merlitz, Holger; Chen, Long
- Macromolecules, Vol. 43, Issue 18
Molecular Dynamics Simulations of Polyelectrolyte Brushes: From Single Chains to Bundles of Chains
journal, December 2007
- Sandberg, Daniel J.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
- Langmuir, Vol. 23, Issue 25
A numerical study of spherical polyelectrolyte brushes by the self-consistent field theory
journal, December 2014
- Quan, Guangyan; Wang, Meiling; Tong, Chaohui
- Polymer, Vol. 55, Issue 25
Swelling Behavior of Multiresponsive Poly(methacrylic acid)- block- -poly( N- isopropylacrylamide) Brushes Synthesized Using Surface-Initiated Photoiniferter-Mediated Photopolymerization : Multiresponsive Polymer Brushes
journal, April 2008
- Rahane, Santosh B.; Floyd, J. Alaina; Metters, Andrew T.
- Advanced Functional Materials, Vol. 18, Issue 8
Direct polymerization of surface-tethered polyelectrolyte layers in aqueous solution via surface-confined atom transfer radical polymerization
journal, January 2007
- Sankhe, Amit Y.; Husson, Scott M.; Kilbey, S. Michael
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 4
Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates: 1. Experiment
journal, November 2007
- Wu, Tao; Gong, Peng; Szleifer, Igal
- Macromolecules, Vol. 40, Issue 24, p. 8756-8764
Spherical polyelectrolyte brushes
journal, October 2007
- Ballauff, M.
- Progress in Polymer Science, Vol. 32, Issue 10
Polyelectrolyte brushes
journal, December 2006
- Ballauff, Matthias; Borisov, Oleg
- Current Opinion in Colloid & Interface Science, Vol. 11, Issue 6
Spherical polyelectrolyte brushes: Comparison between annealed and quenched brushes
journal, October 2001
- Guo, X.; Ballauff, M.
- Physical Review E, Vol. 64, Issue 5
Synthesis of Poly(styrene sulfonate) Brushes
journal, April 2001
- Tran, Y.; Auroy, P.
- Journal of the American Chemical Society, Vol. 123, Issue 16
Determination of the Structure of Polyelectrolyte Brushes
journal, December 1999
- Tran, Y.; Auroy, P.; Lee, L-T.
- Macromolecules, Vol. 32, Issue 26
Density Profile of Polyelectrolyte Brushes
journal, October 1995
- Mir, Y.; Auroy, P.; Auvray, L.
- Physical Review Letters, Vol. 75, Issue 15
Charged Polymer Brushes: Counterion Incorporation and Scaling Relations
journal, November 1998
- Ahrens, Heiko; Förster, Stephan; Helm, Christiane A.
- Physical Review Letters, Vol. 81, Issue 19
Polyelectrolyte Brushes Grafted at the Air/Water Interface
journal, December 1997
- Ahrens, Heiko; Förster, Stephan; Helm, Christiane A.
- Macromolecules, Vol. 30, Issue 26
Rodlike Behavior of Polyelectrolyte Brushes
journal, November 1998
- Guenoun, P.; Muller, F.; Delsanti, M.
- Physical Review Letters, Vol. 81, Issue 18
A polyelectrolyte brush theory
journal, November 1989
- Misra, Sanjay; Varanasi, Sasidhar; Varanasi, P. P.
- Macromolecules, Vol. 22, Issue 11
Segment density profiles of polyelectrolyte brushes determined by Fourier transform ellipsometry
journal, October 1999
- Biesalski, Markus; Rühe, Jürgen; Johannsmann, Diethelm
- The Journal of Chemical Physics, Vol. 111, Issue 15
Polyacrylic Acid Brushes: Surface Pressure and Salt-Induced Swelling
journal, October 2000
- Currie, E. P. K.; Sieval, A. B.; Fleer, G. J.
- Langmuir, Vol. 16, Issue 22
Weak Polyacid Brushes: Preparation by LB Deposition and Optically Detected Titrations
journal, October 1999
- Currie, E. P. K.; Sieval, A. B.; Avena, M.
- Langmuir, Vol. 15, Issue 21
Synthesis of Spherical Polyelectrolyte Brushes by Photoemulsion Polymerization
journal, September 1999
- Guo, X.; Weiss, A.; Ballauff, M.
- Macromolecules, Vol. 32, Issue 19
Hydration in Weak Polyelectrolyte Brushes
journal, April 2013
- Deodhar, Chaitra; Soto-Cantu, Erick; Uhrig, David
- ACS Macro Letters, Vol. 2, Issue 5
Born energy, acid-base equilibrium, structure and interactions of end-grafted weak polyelectrolyte layers
journal, January 2014
- Nap, R. J.; Tagliazucchi, M.; Szleifer, I.
- The Journal of Chemical Physics, Vol. 140, Issue 2
Phase Behavior and Charge Regulation of Weak Polyelectrolyte Grafted Layers
journal, January 2007
- Gong, Peng; Genzer, Jan; Szleifer, I.
- Physical Review Letters, Vol. 98, Issue 1
Self-Consistent Field Theory Study of the Effect of Grafting Density on the Height of a Weak Polyelectrolyte Brush
journal, August 2009
- Witte, Kevin N.; Kim, Sangtae; Won, You-Yeon
- The Journal of Physical Chemistry B, Vol. 113, Issue 32
Charge regulation and local dielectric function in planar polyelectrolyte brushes
journal, June 2012
- Kumar, Rajeev; Sumpter, Bobby G.; Kilbey, S. Michael
- The Journal of Chemical Physics, Vol. 136, Issue 23
Semianalytical Continuum Model for Nondilute Neutral and Charged Brushes Including Finite Stretching
journal, August 2008
- Biesheuvel, P. M.; de Vos, W. M.; Amoskov, V. M.
- Macromolecules, Vol. 41, Issue 16
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
Neutron Reflectivity Study of the Density Profile of a Model End-Grafted Polymer Brush: Influence of Solvent Quality
journal, December 1994
- Karim, A.; Satija, S. K.; Douglas, J. F.
- Physical Review Letters, Vol. 73, Issue 25
Novel evaluation method of neutron reflectivity data applied to stimulus-responsive polymer brushes
journal, January 2008
- Zhang, Jianming; Nylander, Tommy; Campbell, Richard A.
- Soft Matter, Vol. 4, Issue 3
Thickness and Density Profiles of Polyelectrolyte Brushes: Dependence on Grafting Density and Salt Concentration
journal, September 2004
- Romet-Lemonne, G.; Daillant, J.; Guenoun, P.
- Physical Review Letters, Vol. 93, Issue 14
Effects of polydispersity in the end-grafted polymer brush
journal, March 1989
- Milner, S. T.; Witten, T. A.; Cates, M. E.
- Macromolecules, Vol. 22, Issue 2
Modeling the structure of a polydisperse polymer brush
journal, January 2009
- de Vos, Wiebe M.; Leermakers, Frans A. M.
- Polymer, Vol. 50, Issue 1
Microphase separation in thin films of lamellar forming polydisperse di-block copolymers
journal, January 2015
- Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.
- RSC Advances, Vol. 5, Issue 27
Neutron Reflectivity Study of the Structure of pH-Responsive Polymer Brushes Grown from a Macroinitiator at the Sapphire−Water Interface
journal, August 2010
- Moglianetti, Mauro; Webster, John R. P.; Edmondson, Steve
- Langmuir, Vol. 26, Issue 15
GenMin: An enhanced genetic algorithm for global optimization
journal, June 2008
- Tsoulos, Ioannis G.; Lagaris, I. E.
- Computer Physics Communications, Vol. 178, Issue 11
Redox and Acid−Base Coupling in Ultrathin Polyelectrolyte Films
journal, March 2008
- Tagliazucchi, Mario; Calvo, Ernesto J.; Szleifer, Igal
- Langmuir, Vol. 24, Issue 6
Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions
journal, March 2010
- Tagliazucchi, M.; de la Cruz, M. O.; Szleifer, I.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 12
Theoretical Prediction of p K a Values for Methacrylic Acid Oligomers Using Combined Quantum Mechanical and Continuum Solvation Methods
journal, December 2008
- Dong, Haitao; Du, Hongbo; Qian, Xianghong
- The Journal of Physical Chemistry A, Vol. 112, Issue 49
Dipole moment and conformational properties of poly(methacrylic acid) in solvents with hydrogen bonding
journal, April 2006
- Stepanova, T. P.; Philippova, O. E.
- Polymer Science Series A, Vol. 48, Issue 4
Dielectric polarization of a partially neutralized poly(methacrylic acid) in dilute aqueous solutions: Conformational transition
journal, March 2006
- Stepanova, T. P.; Filippova, O. E.
- Polymer Science Series A, Vol. 48, Issue 3
Entropic Elasticity of Single Polymer Chains of Poly(methacrylic acid) Measured by Atomic Force Microscopy
journal, February 1999
- Ortiz, C.; Hadziioannou, G.
- Macromolecules, Vol. 32, Issue 3
Synthesis, characterization and swelling behaviour of poly(methacrylic acid) brushes synthesized using atom transfer radical polymerization
journal, February 2009
- Parnell, Andrew J.; Martin, Simon J.; Dang, Cheen C.
- Polymer, Vol. 50, Issue 4
Surface Studies of Solids by Total Reflection of X-Rays
journal, July 1954
- Parratt, L. G.
- Physical Review, Vol. 95, Issue 2
Works referencing / citing this record:
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journal, January 2019
- Landsgesell, Jonas; Nová, Lucie; Rud, Oleg
- Soft Matter, Vol. 15, Issue 6
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journal, January 2019
- Sachar, Harnoor Singh; Sivasankar, Vishal Sankar; Das, Siddhartha
- Soft Matter, Vol. 15, Issue 4
Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush
journal, October 2018
- Mahalik, Jyoti P.; Sumpter, Bobby G.; Kumar, Rajeev
- The Journal of Chemical Physics, Vol. 149, Issue 16
Enhanced scattering induced by electrostatic correlations in concentrated solutions of salt-free dipolar and ionic polymers
journal, October 2018
- Kumar, Rajeev; Lokitz, Bradley; Long, Timothy E.
- The Journal of Chemical Physics, Vol. 149, Issue 16
Behavior of Weak Polyelectrolyte Brushes in Mixed Salt Solutions
journal, January 2018
- Willott, Joshua D.; Murdoch, Timothy J.; Leermakers, Frans A. M.
- Macromolecules, Vol. 51, Issue 3