Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush
Abstract
The effects of added salt on a planar dipolar polymer brush immersed in a polar solvent are studied using a field theoretic approach. The field theory developed in this work provides a unified framework for capturing effects of the inhomogeneous dielectric function, translational entropy of ions, crowding due to finite sized ions, ionic size asymmetry, and ion solvation. In this paper, we use the theory to study the effects of ion sizes, their concentration, and ion-solvation on the polymer segment density profiles of a dipolar brush immersed in a solution containing symmetric salt ions. The interplay of crowding effects, translational entropy, and ion solvation is shown to exhibit either an increase or decrease in the brush height. Translational entropy and crowding effects due to finite sizes of the ions tend to cause expansion of the brush as well as uniform distribution of the ions. By contrast, ion-solvation effects, which tend to be stronger for smaller ions, are shown to cause shrinkage of the brush and inhomogeneous distribution of the ions.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1474514
- Alternate Identifier(s):
- OSTI ID: 1465614
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 149; Journal Issue: 16; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Mahalik, Jyoti P., Sumpter, Bobby G., and Kumar, Rajeev. Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush. United States: N. p., 2018.
Web. doi:10.1063/1.5037077.
Mahalik, Jyoti P., Sumpter, Bobby G., & Kumar, Rajeev. Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush. United States. https://doi.org/10.1063/1.5037077
Mahalik, Jyoti P., Sumpter, Bobby G., and Kumar, Rajeev. Tue .
"Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush". United States. https://doi.org/10.1063/1.5037077. https://www.osti.gov/servlets/purl/1474514.
@article{osti_1474514,
title = {Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush},
author = {Mahalik, Jyoti P. and Sumpter, Bobby G. and Kumar, Rajeev},
abstractNote = {The effects of added salt on a planar dipolar polymer brush immersed in a polar solvent are studied using a field theoretic approach. The field theory developed in this work provides a unified framework for capturing effects of the inhomogeneous dielectric function, translational entropy of ions, crowding due to finite sized ions, ionic size asymmetry, and ion solvation. In this paper, we use the theory to study the effects of ion sizes, their concentration, and ion-solvation on the polymer segment density profiles of a dipolar brush immersed in a solution containing symmetric salt ions. The interplay of crowding effects, translational entropy, and ion solvation is shown to exhibit either an increase or decrease in the brush height. Translational entropy and crowding effects due to finite sizes of the ions tend to cause expansion of the brush as well as uniform distribution of the ions. By contrast, ion-solvation effects, which tend to be stronger for smaller ions, are shown to cause shrinkage of the brush and inhomogeneous distribution of the ions.},
doi = {10.1063/1.5037077},
journal = {Journal of Chemical Physics},
number = 16,
volume = 149,
place = {United States},
year = {Tue Aug 21 00:00:00 EDT 2018},
month = {Tue Aug 21 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Synthesis and properties of stimuli-sensitive heterografted toothbrush-like terpolymers with a linear handle and two types of V-shaped grafts
journal, January 2016
- Tong, Min; An, Xiaonan; Pan, Weidong
- Polymer Chemistry, Vol. 7, Issue 12
Negligible Effect of Ions on the Hydrogen-Bond Structure in Liquid Water
journal, July 2003
- Omta, A. W.
- Science, Vol. 301, Issue 5631
Statistical field theory description of inhomogeneous polarizable soft matter
journal, October 2016
- Martin, Jonathan M.; Li, Wei; Delaney, Kris T.
- The Journal of Chemical Physics, Vol. 145, Issue 15
Grafting of thermosensitive poly(N-isopropylacrylamide) from wet bacterial cellulose sheets to improve its swelling-drying ability
journal, November 2016
- Alosmanov, Rasim; Wolski, Karol; Zapotoczny, Szczepan
- Cellulose, Vol. 24, Issue 1
Ab Initio Molar Volumes and Gaussian Radii
journal, February 2009
- Parsons, Drew F.; Ninham, Barry W.
- The Journal of Physical Chemistry A, Vol. 113, Issue 6
Thermodynamic Description of Hofmeister Effects on the LCST of Thermosensitive Polymers
journal, September 2014
- Heyda, Jan; Dzubiella, Joachim
- The Journal of Physical Chemistry B, Vol. 118, Issue 37
Chain mobility and film softness mediated protein antifouling at the solid–liquid interface
journal, January 2016
- Liu, Dan; Guo, Juan; Zhang, Jing-Hui
- Journal of Materials Chemistry B, Vol. 4, Issue 36
Computation of multiphase systems with phase field models
journal, September 2003
- Badalassi, V. E.; Ceniceros, H. D.; Banerjee, S.
- Journal of Computational Physics, Vol. 190, Issue 2
Nanostructure of Poly( N -isopropylacrylamide) Brush at the Air/Water Interface and Its Responsivity to Temperature and Salt
journal, August 2016
- Matsuoka, Hideki; Uda, Kyohei
- Langmuir, Vol. 32, Issue 33
Synthesis of Well-Defined Environmentally Responsive Polymer Brushes by Aqueous ATRP
journal, February 2004
- Kizhakkedathu, Jayachandran N.; Norris-Jones, Raymond; Brooks, Donald E.
- Macromolecules, Vol. 37, Issue 3
Salt-Induced Depression of Lower Critical Solution Temperature in a Surface-Grafted Neutral Thermoresponsive Polymer
journal, May 2006
- Jhon, Young K.; Bhat, Rajendra R.; Jeong, Changwoo
- Macromolecular Rapid Communications, Vol. 27, Issue 9
Electric Moments of Molecules in Liquids
journal, August 1936
- Onsager, Lars
- Journal of the American Chemical Society, Vol. 58, Issue 8
The Dielectric Constant of Water and the Saturation Effect
journal, April 1951
- Booth, F.
- The Journal of Chemical Physics, Vol. 19, Issue 4
Temperature-Sensitive, Fluorescent Poly(N-Isopropyl-acrylamide)-Grafted Cellulose Nanocrystals for Drug Release
journal, May 2016
- Wu, Weibing; Li, Jian; Liu, Wei
- BioResources, Vol. 11, Issue 3
Theoretically informed coarse grain simulations of polymeric systems
journal, August 2009
- Pike, Darin Q.; Detcheverry, François A.; Müller, Marcus
- The Journal of Chemical Physics, Vol. 131, Issue 8
Water Content of Hydrated Polymer Brushes Measured by an In Situ Combination of a Quartz Crystal Microbalance with Dissipation Monitoring and Spectroscopic Ellipsometry
journal, November 2011
- Ramos, Jagoba J. Iturri; Moya, Sergio E.
- Macromolecular Rapid Communications, Vol. 32, Issue 24
Hydration and Mobility of Poly(ethylene oxide) Brushes
journal, August 2017
- Dahal, Udaya R.; Wang, Zilu; Dormidontova, Elena E.
- Macromolecules, Vol. 50, Issue 17
Enhanced Phase Segregation Induced by Dipolar Interactions in Polymer Blends
journal, September 2014
- Kumar, Rajeev; Sumpter, Bobby G.; Muthukumar, M.
- Macromolecules, Vol. 47, Issue 18
Vertical Phase Segregation Induced by Dipolar Interactions in Planar Polymer Brushes
journal, September 2016
- Mahalik, Jyoti P.; Sumpter, Bobby G.; Kumar, Rajeev
- Macromolecules, Vol. 49, Issue 18
Responsive Behaviors of Diblock Polyampholyte Brushes within Self-Consistent Field Theory
journal, December 2011
- Qu, Li-Jian; Man, Xingkun; Han, Charles C.
- The Journal of Physical Chemistry B, Vol. 116, Issue 2
Attraction between Opposing Planar Dipolar Polymer Brushes
journal, August 2017
- Mahalik, J. P.; Sumpter, Bobby G.; Kumar, Rajeev
- Langmuir, Vol. 33, Issue 36
Effects of Ion Solvation on the Miscibility of Binary Polymer Blends †
journal, December 2008
- Wang, Zhen-Gang
- The Journal of Physical Chemistry B, Vol. 112, Issue 50
Impact of Protein Denaturants and Stabilizers on Water Structure
journal, February 2004
- Batchelor, Joseph D.; Olteanu, Alina; Tripathy, Ashutosh
- Journal of the American Chemical Society, Vol. 126, Issue 7
Implicit-Explicit Methods for Time-Dependent Partial Differential Equations
journal, June 1995
- Ascher, Uri M.; Ruuth, Steven J.; Wetton, Brian T. R.
- SIAM Journal on Numerical Analysis, Vol. 32, Issue 3
Specificity in Cationic Interaction with Poly( N -isopropylacrylamide)
journal, April 2013
- Du, Hongbo; Wickramasinghe, Sumith Ranil; Qian, Xianghong
- The Journal of Physical Chemistry B, Vol. 117, Issue 17
Effect of Grafting Density on Phase Transition Behavior for Poly( N -isopropylacryamide) Brushes in Aqueous Solutions Studied by AFM and QCM-D
journal, September 2010
- Ishida, Naoyuki; Biggs, Simon
- Macromolecules, Vol. 43, Issue 17
Influence of Additives on the Thermoresponsive Behavior of Polymers in Aqueous Solution
journal, November 2005
- Van Durme, Kurt; Rahier, Hubert; Van Mele, Bruno
- Macromolecules, Vol. 38, Issue 24
Polymer brush-based optical device with multiple responsivities
journal, January 2015
- Wei, Menglian; Gao, Yongfeng; Serpe, Michael J.
- Journal of Materials Chemistry B, Vol. 3, Issue 5
Temperature and pH Dual-Responsive Core-Brush Nanocomposite for Enrichment of Glycoproteins
journal, March 2017
- Jiang, Lingdong; Messing, Maria E.; Ye, Lei
- ACS Applied Materials & Interfaces, Vol. 9, Issue 10
Electrochemically produced responsive hydrogel films: Influence of added salt on thickness and morphology
journal, October 2008
- Bünsow, Johanna; Johannsmann, Diethelm
- Journal of Colloid and Interface Science, Vol. 326, Issue 1
On the Mechanism of the Hofmeister Effect
journal, September 2004
- Gurau, Marc C.; Lim, Soon-Mi; Castellana, Edward T.
- Journal of the American Chemical Society, Vol. 126, Issue 34
Synthesis of Well-Defined Amphiphilic Diblock Copolymer Brushes on Halloysite Nanotubes via Surface-Initiated Reversible Addition-Fragmentation Chain Transfer Polymerization
journal, August 2017
- Bach, Long Giang; Ho, Van Thi Thanh; Quynh, Bui Thi Phuong
- Journal of Nanoscience and Nanotechnology, Vol. 17, Issue 8
Effects of Salt on the Lower Critical Solution Temperature of Poly ( N -Isopropylacrylamide)
journal, December 2010
- Du, Hongbo; Wickramasinghe, Ranil; Qian, Xianghong
- The Journal of Physical Chemistry B, Vol. 114, Issue 49
Polyelectrolyte brushes with specific charge distribution: Mean-field lattice theory
journal, April 2001
- Shusharina, N. P.; Linse, P.
- The European Physical Journal E, Vol. 4, Issue 4
Fluctuation in electrolyte solutions: The self energy
journal, February 2010
- Wang, Zhen-Gang
- Physical Review E, Vol. 81, Issue 2
Preparation of Soft Hydrogel Nanoparticles with PNIPAm Hair and Characterization of Their Temperature-Induced Aggregation
journal, February 2010
- Lv, Shengjie; Liu, Lianying; Yang, Wantai
- Langmuir, Vol. 26, Issue 3
Bacterial adhesion and growth on a polymer brush-coating
journal, October 2008
- Nejadnik, M. Reza; van der Mei, Henny C.; Norde, Willem
- Biomaterials, Vol. 29, Issue 30
Specific Ion Effects on the Water Solubility of Macromolecules: PNIPAM and the Hofmeister Series
journal, October 2005
- Zhang, Yanjie; Furyk, Steven; Bergbreiter, David E.
- Journal of the American Chemical Society, Vol. 127, Issue 41
Surface Grafting of PEO-Based Star-Shaped Molecules for Bioanalytical and Biomedical Applications
journal, August 2007
- Gasteier, Peter; Reska, Anna; Schulte, Petra
- Macromolecular Bioscience, Vol. 7, Issue 8
Oppositely charged polyelectrolytes grafted onto planar surface: Mean-field lattice theory
journal, October 2001
- Shusharina, N. P.; Linse, P.
- The European Physical Journal E, Vol. 6, Issue 2
PNIPAM grafted surfaces through ATRP and RAFT polymerization: Chemistry and bioadhesion
journal, March 2017
- Conzatti, G.; Cavalie, S.; Combes, C.
- Colloids and Surfaces B: Biointerfaces, Vol. 151
Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes
journal, March 2016
- Mahalik, J. P.; Yang, Yubo; Deodhar, Chaitra
- Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 10
Salt-Induced Structural Behavior for Poly( N -isopropylacryamide) Grafted onto Solid Surface Observed Directly by AFM and QCM-D
journal, December 2007
- Ishida, Naoyuki; Biggs, Simon
- Macromolecules, Vol. 40, Issue 25
Molecular dynamics simulations of oligoester brushes: the origin of unusual conformations
journal, January 2017
- Glova, A. D.; Larin, S. V.; Falkovich, S. G.
- Soft Matter, Vol. 13, Issue 37
Ion-specific swelling behavior of poly(ethylene oxide) gel and the correlation to the intrinsic viscosity of the polymer in salt solutions
journal, June 2002
- Masuda, Yoko; Nakanishi, Tadashi
- Colloid & Polymer Science, Vol. 280, Issue 6
Novel Alkali Activation of Titanium Substrates To Grow Thick and Covalently Bound PMMA Layers
journal, January 2018
- Reggente, Melania; Masson, Patrick; Dollinger, Camille
- ACS Applied Materials & Interfaces, Vol. 10, Issue 6
A review on thermoresponsive cell culture systems based on poly( N -isopropylacrylamide) and derivatives
journal, July 2017
- Li, Jiaxing; Fan, Xiaoguang; Yang, Lei
- International Journal of Polymeric Materials and Polymeric Biomaterials, Vol. 67, Issue 6
Temperature-Responsive Hierarchical Polymer Brushes Switching from Bactericidal to Cell Repellency
journal, November 2017
- Wang, Xianghong; Yan, Shunjie; Song, Lingjie
- ACS Applied Materials & Interfaces, Vol. 9, Issue 46
Reversible Protein Adsorption on Mixed PEO/PAA Polymer Brushes: Role of Ionic Strength and PEO Content
journal, February 2018
- Bratek-Skicki, Anna; Eloy, Pierre; Morga, Maria
- Langmuir, Vol. 34, Issue 9
Regularly grafted polymer brush with degradable PCL backbone by ring-opening polymerization and “click” reaction: synthesis and self-assembly
journal, January 2016
- Chang, Ruixue; Qin, Jianglei; Wang, Haijun
- Journal of Polymer Research, Vol. 23, Issue 2
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
Salt Effects in the Cononsolvency of Poly(N-isopropylacrylamide) Microgels
journal, January 2010
- López-León, Teresa; Bastos-González, Delfina; Ortega-Vinuesa, Juan Luis
- ChemPhysChem, Vol. 11, Issue 1
Grafting Polymerization of N-isopropylacrylamide on the Surfaces of Silica by ATRP and Its Application in HPLC
journal, March 2010
- Ni, Caihua; Wang, Wentao; Zhu, Changping
- Soft Materials, Vol. 8, Issue 1
Chain Conformation of a New Class of PEG-Based Thermoresponsive Polymer Brushes Grafted on Silicon as Determined by Neutron Reflectometry
journal, September 2009
- Gao, Xiang; Kučerka, Norbert; Nieh, Mu-Ping
- Langmuir, Vol. 25, Issue 17
PEO-based brush-type amphiphilic macro-RAFT agents and their assembled polyHIPE monolithic structures for applications in separation science
journal, August 2017
- Khodabandeh, Aminreza; Arrua, R. Dario; Mansour, Fotouh R.
- Scientific Reports, Vol. 7, Issue 1
Synthesis of naringin-based polymer brushes via se ATRP
journal, August 2017
- Chmielarz, Paweł
- Polymers for Advanced Technologies, Vol. 29, Issue 1
Utilization of star-shaped polymer architecture in the creation of high-density polymer brush coatings for the prevention of platelet and bacteria adhesion
journal, January 2014
- Totani, Masayasu; Ando, Tsuyoshi; Terada, Kayo
- Biomaterials Science, Vol. 2, Issue 9
Poly(N-isopropylacrylamide): experiment, theory and application
journal, January 1992
- Schild, H. G.
- Progress in Polymer Science, Vol. 17, Issue 2, p. 163-249
Charge regulation and local dielectric function in planar polyelectrolyte brushes
text, January 2012
- Kumar, Rajeev; Sumpter, Bobby G.; Kilbey, S. Michael
- arXiv
Enhanced phase segregation induced by dipolar interactions in polymer blends
text, January 2014
- Kumar, Rajeev; Sumpter, Bobby G.; Muthukumar, M.
- arXiv