The effect of chain stiffness and salt on the elastic response of a polyelectrolyte
Abstract
Here, We present simulations of the force-extension curves of strong polyelectrolytes with varying intrinsic stiffness as well as specifically treating hyaluronic acid, a polyelectrolyte of intermediate stiffness. Whereas fully flexible polyelectrolytes show a high-force regime where extension increases nearly logarithmically with force, we find that the addition of even a small amount of stiffness alters the short-range structure and removes this logarithmic elastic regime. This further confirms that the logarithmic regime is a consequence of the short-ranged “wrinkles” in the flexible chain. As the stiffness increases, the force-extension curves tend toward and reach the wormlike chain behavior. Using the screened Coulomb potential and a simple bead-spring model, the simulations are able to reproduce the hyaluronic acid experimental force-extension curves for salt concentrations ranging from 1 to 500 mM. Furthermore, the simulation data can be scaled to a universal curve like the experimental data. The scaling analysis is consistent with the interpretation that, in the low-salt limit, the hyaluronic acid chain stiffness scales with salt with an exponent of –0.7, rather than either of the two main theoretical predictions of –0.5 and –1. Furthermore, given the conditions of the simulation, we conclude that this exponent value is not due to counterionmore »
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Univ. of California, Santa Barbara, CA (United States); Brandeis Univ., Waltham, MA (United States)
- Univ. of California, Santa Barbara, CA (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1473953
- Alternate Identifier(s):
- OSTI ID: 1461567
- Report Number(s):
- SAND-2018-9832J
Journal ID: ISSN 0021-9606; 667684
- Grant/Contract Number:
- AC04-94AL85000; NA0003525
- 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
Stevens, Mark J., Berezney, John P., and Saleh, Omar A. The effect of chain stiffness and salt on the elastic response of a polyelectrolyte. United States: N. p., 2018.
Web. doi:10.1063/1.5035340.
Stevens, Mark J., Berezney, John P., & Saleh, Omar A. The effect of chain stiffness and salt on the elastic response of a polyelectrolyte. United States. https://doi.org/10.1063/1.5035340
Stevens, Mark J., Berezney, John P., and Saleh, Omar A. Tue .
"The effect of chain stiffness and salt on the elastic response of a polyelectrolyte". United States. https://doi.org/10.1063/1.5035340. https://www.osti.gov/servlets/purl/1473953.
@article{osti_1473953,
title = {The effect of chain stiffness and salt on the elastic response of a polyelectrolyte},
author = {Stevens, Mark J. and Berezney, John P. and Saleh, Omar A.},
abstractNote = {Here, We present simulations of the force-extension curves of strong polyelectrolytes with varying intrinsic stiffness as well as specifically treating hyaluronic acid, a polyelectrolyte of intermediate stiffness. Whereas fully flexible polyelectrolytes show a high-force regime where extension increases nearly logarithmically with force, we find that the addition of even a small amount of stiffness alters the short-range structure and removes this logarithmic elastic regime. This further confirms that the logarithmic regime is a consequence of the short-ranged “wrinkles” in the flexible chain. As the stiffness increases, the force-extension curves tend toward and reach the wormlike chain behavior. Using the screened Coulomb potential and a simple bead-spring model, the simulations are able to reproduce the hyaluronic acid experimental force-extension curves for salt concentrations ranging from 1 to 500 mM. Furthermore, the simulation data can be scaled to a universal curve like the experimental data. The scaling analysis is consistent with the interpretation that, in the low-salt limit, the hyaluronic acid chain stiffness scales with salt with an exponent of –0.7, rather than either of the two main theoretical predictions of –0.5 and –1. Furthermore, given the conditions of the simulation, we conclude that this exponent value is not due to counterion condensation effects, as had previously been suggested.},
doi = {10.1063/1.5035340},
journal = {Journal of Chemical Physics},
number = 16,
volume = 149,
place = {United States},
year = {Tue Jul 24 00:00:00 EDT 2018},
month = {Tue Jul 24 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Polyelectrolytes near the rod limit
journal, March 1977
- Odijk, Theo
- Journal of Polymer Science: Polymer Physics Edition, Vol. 15, Issue 3
Nonlinear Low-Force Elasticity of Single-Stranded DNA Molecules
journal, February 2009
- Saleh, O. A.; McIntosh, D. B.; Pincus, P.
- Physical Review Letters, Vol. 102, Issue 6
Variational theory for a single polyelectrolyte chain revisited
journal, May 2004
- Manghi, M.; Netz, R. R.
- The European Physical Journal E, Vol. 14, Issue 1
Effect of the Electrostatic Interactions on Stretching of Semiflexible and Biological Polyelectrolytes
journal, March 2010
- Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
- Macromolecules, Vol. 43, Issue 5
Excluded Volume Effects and Stretched Polymer Chains
journal, May 1976
- Pincus, P.
- Macromolecules, Vol. 9, Issue 3
Detailed scaling analysis of low-force polyelectrolyte elasticity
journal, October 2009
- McIntosh, D. B.; Ribeck, N.; Saleh, O. A.
- Physical Review E, Vol. 80, Issue 4
Structure of Salt-free Linear Polyelectrolytes in the Debye-Hückel Approximation
journal, November 1996
- Stevens, Mark J.; Kremer, Kurt
- Journal de Physique II, Vol. 6, Issue 11
Simulations of Stretching a Strong, Flexible Polyelectrolyte
journal, July 2012
- Stevens, Mark J.; McIntosh, Dustin B.; Saleh, Omar A.
- Macromolecules, Vol. 45, Issue 14
On the theory of weakly charged polyelectrolytes
journal, November 1982
- Khokhlov, A. R.; Khachaturian, K. A.
- Polymer, Vol. 23, Issue 12
Electrostatic Persistence Length of a Wormlike Polyelectrolyte
journal, September 1977
- Skolnick, Jeffrey; Fixman, Marshall
- Macromolecules, Vol. 10, Issue 5
Stretching DNA
journal, December 1995
- Marko, John F.; Siggia, Eric D.
- Macromolecules, Vol. 28, Issue 26
Simulations of Stretching a Strong, Flexible Polyelectrolyte: Using Long Chains To Access the Pincus Scaling Regime
journal, July 2013
- Stevens, Mark J.; McIntosh, Dustin B.; Saleh, Omar A.
- Macromolecules, Vol. 46, Issue 15
Stretching Single Stranded DNA, a Model Polyelectrolyte
journal, November 2002
- Dessinges, M. -N.; Maier, B.; Zhang, Y.
- Physical Review Letters, Vol. 89, Issue 24
The pivot algorithm: A highly efficient Monte Carlo method for the self-avoiding walk
journal, January 1988
- Madras, Neal; Sokal, Alan D.
- Journal of Statistical Physics, Vol. 50, Issue 1-2
Persistence Length of Polyelectrolyte Chains
journal, November 1993
- Barrat, J. -L; Joanny, J. -F
- Europhysics Letters (EPL), Vol. 24, Issue 5
Elastic Properties of a Single-Stranded Charged Homopolymeric Ribonucleotide
journal, September 2004
- Seol, Yeonee; Skinner, Gary M.; Visscher, Koen
- Physical Review Letters, Vol. 93, Issue 11
Single-stranded nucleic acid elasticity arises from internal electrostatic tension
journal, May 2017
- Jacobson, David R.; McIntosh, Dustin B.; Stevens, Mark J.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 20
Electrostatic Effects on the Conformation and Elasticity of Hyaluronic Acid, a Moderately Flexible Polyelectrolyte
journal, January 2017
- Berezney, John P.; Saleh, Omar A.
- Macromolecules, Vol. 50, Issue 3
Electrostatic Persistence Length of a Polyelectrolyte Chain
journal, March 1995
- Ha, B. -Y.; Thirumalai, D.
- Macromolecules, Vol. 28, Issue 2
Configurational properties of a single semiflexible polyelectrolyte
journal, September 2001
- Ghosh, K.; Carri, Gustavo A.; Muthukumar, M.
- The Journal of Chemical Physics, Vol. 115, Issue 9
Salt Species-Dependent Electrostatic Effects on ssDNA Elasticity
journal, April 2011
- McIntosh, D. B.; Saleh, O. A.
- Macromolecules, Vol. 44, Issue 7
Variational charge renormalization in charged systems
journal, July 2003
- Netz, R. R.; Orland, H.
- The European Physical Journal E, Vol. 11, Issue 3
Electrostatic Persistence Length of Semiflexible and Flexible Polyelectrolytes
journal, November 2005
- Dobrynin, Andrey V.
- Macromolecules, Vol. 38, Issue 22
The electrostatic persistence length calculated from Monte Carlo, variational and perturbation methods
journal, July 1997
- Ullner, Magnus; Jönsson, Bo; Peterson, Carsten
- The Journal of Chemical Physics, Vol. 107, Issue 4
Simulations of stretching a flexible polyelectrolyte with varying charge separation
journal, July 2016
- Stevens, M. J.; Saleh, O. A.
- The European Physical Journal Special Topics, Vol. 225, Issue 8-9
Swelling of biological and semiflexible polyelectrolytes
journal, September 2009
- Dobrynin, Andrey V.; Carrillo, Jan-Michael Y.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 42
Single-stranded nucleic acid elasticity arises from internal electrostatic tension
text, January 2017
- B., McIntosh, Dustin; A., Saleh, Omar; R., Jacobson, David
- The University of North Carolina at Chapel Hill University Libraries
Works referencing / citing this record:
Soft condensed matter physics of foods and macronutrients
journal, July 2019
- Assenza, Salvatore; Mezzenga, Raffaele
- Nature Reviews Physics, Vol. 1, Issue 9
Polyelectrolyte Conformation Controlled by a Trivalent-Rich Ion Jacket
journal, October 2019
- Innes-Gold, Sarah N.; Pincus, Philip A.; Stevens, Mark J.
- Physical Review Letters, Vol. 123, Issue 18
Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes
journal, November 2019
- Blanco, Pablo M.; Madurga, Sergio; Narambuena, Claudio F.
- Polymers, Vol. 11, Issue 12