The effect of chain stiffness and salt on the elastic response of a polyelectrolyte

Stevens, Mark J.; Berezney, John P.; Saleh, Omar A.

doi:10.1063/1.5035340

The effect of chain stiffness and salt on the elastic response of a polyelectrolyte

Journal Article · Tue Jul 24 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5035340· OSTI ID:1473953

Stevens, Mark J. ^[1]; Berezney, John P. ^[2]; ^[3]

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)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1473953

Alternate ID(s):: OSTI ID: 1461567

Report Number(s):: SAND--2018-9832J; 667684

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 149; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (27)

Polyelectrolytes near the rod limit Odijk, Theo Journal of Polymer Science: Polymer Physics Edition, Vol. 15, Issue 3 https://doi.org/10.1002/pol.1977.180150307	journal	March 1977
The pivot algorithm: A highly efficient Monte Carlo method for the self-avoiding walk Madras, Neal; Sokal, Alan D. Journal of Statistical Physics, Vol. 50, Issue 1-2 https://doi.org/10.1007/bf01022990	journal	January 1988
On the theory of weakly charged polyelectrolytes Khokhlov, A. R.; Khachaturian, K. A. Polymer, Vol. 23, Issue 12 https://doi.org/10.1016/0032-3861(82)90116-1	journal	November 1982
Electrostatic Effects on the Conformation and Elasticity of Hyaluronic Acid, a Moderately Flexible Polyelectrolyte Berezney, John P.; Saleh, Omar A. Macromolecules, Vol. 50, Issue 3 https://doi.org/10.1021/acs.macromol.6b02166	journal	January 2017
Electrostatic Persistence Length of a Polyelectrolyte Chain Ha, B. -Y.; Thirumalai, D. Macromolecules, Vol. 28, Issue 2 https://doi.org/10.1021/ma00106a023	journal	March 1995
Stretching DNA Marko, John F.; Siggia, Eric D. Macromolecules, Vol. 28, Issue 26 https://doi.org/10.1021/ma00130a008	journal	December 1995
Electrostatic Persistence Length of Semiflexible and Flexible Polyelectrolytes Dobrynin, Andrey V. Macromolecules, Vol. 38, Issue 22 https://doi.org/10.1021/ma051353r	journal	November 2005
Salt Species-Dependent Electrostatic Effects on ssDNA Elasticity McIntosh, D. B.; Saleh, O. A. Macromolecules, Vol. 44, Issue 7 https://doi.org/10.1021/ma1028196	journal	April 2011
Simulations of Stretching a Strong, Flexible Polyelectrolyte Stevens, Mark J.; McIntosh, Dustin B.; Saleh, Omar A. Macromolecules, Vol. 45, Issue 14 https://doi.org/10.1021/ma300899x	journal	July 2012
Simulations of Stretching a Strong, Flexible Polyelectrolyte: Using Long Chains To Access the Pincus Scaling Regime Stevens, Mark J.; McIntosh, Dustin B.; Saleh, Omar A. Macromolecules, Vol. 46, Issue 15 https://doi.org/10.1021/ma401211w	journal	July 2013
Excluded Volume Effects and Stretched Polymer Chains Pincus, P. Macromolecules, Vol. 9, Issue 3 https://doi.org/10.1021/ma60051a002	journal	May 1976
Electrostatic Persistence Length of a Wormlike Polyelectrolyte Skolnick, Jeffrey; Fixman, Marshall Macromolecules, Vol. 10, Issue 5 https://doi.org/10.1021/ma60059a011	journal	September 1977
Effect of the Electrostatic Interactions on Stretching of Semiflexible and Biological Polyelectrolytes Carrillo, Jan-Michael Y.; Dobrynin, Andrey V. Macromolecules, Vol. 43, Issue 5 https://doi.org/10.1021/ma902304x	journal	March 2010
Structure of Salt-free Linear Polyelectrolytes in the Debye-Hückel Approximation Stevens, Mark J.; Kremer, Kurt Journal de Physique II, Vol. 6, Issue 11 https://doi.org/10.1051/jp2:1996151	journal	November 1996
Configurational properties of a single semiflexible polyelectrolyte Ghosh, K.; Carri, Gustavo A.; Muthukumar, M. The Journal of Chemical Physics, Vol. 115, Issue 9 https://doi.org/10.1063/1.1386924	journal	September 2001
The electrostatic persistence length calculated from Monte Carlo, variational and perturbation methods Ullner, Magnus; Jönsson, Bo; Peterson, Carsten The Journal of Chemical Physics, Vol. 107, Issue 4 https://doi.org/10.1063/1.474139	journal	July 1997
Single-stranded nucleic acid elasticity arises from internal electrostatic tension Jacobson, David R.; McIntosh, Dustin B.; Stevens, Mark J. Proceedings of the National Academy of Sciences, Vol. 114, Issue 20 https://doi.org/10.1073/pnas.1701132114	journal	May 2017
Swelling of biological and semiflexible polyelectrolytes Dobrynin, Andrey V.; Carrillo, Jan-Michael Y. Journal of Physics: Condensed Matter, Vol. 21, Issue 42 https://doi.org/10.1088/0953-8984/21/42/424112	journal	September 2009
Detailed scaling analysis of low-force polyelectrolyte elasticity McIntosh, D. B.; Ribeck, N.; Saleh, O. A. Physical Review E, Vol. 80, Issue 4 https://doi.org/10.1103/physreve.80.041803	journal	October 2009
Nonlinear Low-Force Elasticity of Single-Stranded DNA Molecules Saleh, O. A.; McIntosh, D. B.; Pincus, P. Physical Review Letters, Vol. 102, Issue 6 https://doi.org/10.1103/physrevlett.102.068301	journal	February 2009
Stretching Single Stranded DNA, a Model Polyelectrolyte Dessinges, M. -N.; Maier, B.; Zhang, Y. Physical Review Letters, Vol. 89, Issue 24 https://doi.org/10.1103/physrevlett.89.248102	journal	November 2002
Elastic Properties of a Single-Stranded Charged Homopolymeric Ribonucleotide Seol, Yeonee; Skinner, Gary M.; Visscher, Koen Physical Review Letters, Vol. 93, Issue 11 https://doi.org/10.1103/physrevlett.93.118102	journal	September 2004
Variational charge renormalization in charged systems Netz, R. R.; Orland, H. The European Physical Journal E, Vol. 11, Issue 3 https://doi.org/10.1140/epje/i2002-10159-0	journal	July 2003
Variational theory for a single polyelectrolyte chain revisited Manghi, M.; Netz, R. R. The European Physical Journal E, Vol. 14, Issue 1 https://doi.org/10.1140/epje/i2004-10007-3	journal	May 2004
Simulations of stretching a flexible polyelectrolyte with varying charge separation Stevens, M. J.; Saleh, O. A. The European Physical Journal Special Topics, Vol. 225, Issue 8-9 https://doi.org/10.1140/epjst/e2016-60113-0	journal	July 2016
Persistence Length of Polyelectrolyte Chains Barrat, J. -L; Joanny, J. -F Europhysics Letters (EPL), Vol. 24, Issue 5 https://doi.org/10.1209/0295-5075/24/5/003	journal	November 1993
Single-stranded nucleic acid elasticity arises from internal electrostatic tension B., McIntosh, Dustin; A., Saleh, Omar; R., Jacobson, David The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/qx77-r728	text	January 2017

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Soft condensed matter physics of foods and macronutrients Assenza, Salvatore; Mezzenga, Raffaele Nature Reviews Physics, Vol. 1, Issue 9 https://doi.org/10.1038/s42254-019-0077-8	journal	July 2019
Polyelectrolyte Conformation Controlled by a Trivalent-Rich Ion Jacket Innes-Gold, Sarah N.; Pincus, Philip A.; Stevens, Mark J. Physical Review Letters, Vol. 123, Issue 18 https://doi.org/10.1103/physrevlett.123.187801	journal	October 2019
Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes Blanco, Pablo M.; Madurga, Sergio; Narambuena, Claudio F. Polymers, Vol. 11, Issue 12 https://doi.org/10.3390/polym11121962	journal	November 2019

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