Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect

Cheng-Jiang Lin; Jun-Jun Wang; Yuan Jiang; Shu-Li Chen; Hong-Fei Li; Wen-Han Zhao; Qing-Rong Huang; Chang-Ru Rong; Xiao-Zheng Duan

doi:10.1007/s10118-024-3105-9

Your Location：

Home >

Browse articles >

Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect

RESEARCH ARTICLE | Updated：2024-08-27

- Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect
- Chinese Journal of Polymer Science Vol. 42, Issue 9, Pages: 1341-1352(2024)
- Affiliations：
  
  a.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
  c.National Key Laboratory of Advanced Vehicle Integration and Control, China FAW Group Co., Ltd., Changchun 130013, China
  d.State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China
  e.Department of Food Science, Rutgers University, 65 Dudley Road, New Brunswick, New Jersey 08901, USA
- Author bio：
  
  hfli@ciac.ac.cn (H.F.L.)
  rongchangru@faw.com.cn (C.R.R.)
  xzduan@ciac.ac.cn (X.Z.D.)
- Funds：
- DOI：10.1007/s10118-024-3105-9
  CLC：
- Received：28 December 2023，
  
  Revised：2024-02-10，
  
  Accepted：20 February 2024，
  
  Online First：03 April 2024，
  
  Published：01 September 2024
- Accepted：
Scan QR Code
Lin, C. J.; Wang, J. J.; Jiang, Y.; Chen, S. L.; Li, H. F.; Zhao, W. H.; Huang, Q. R.; Rong, C. R.; Duan, X. Z. Structural properties of ions and polyelectrolytes in aqueous solutions under external electric fields: the sign effect. Chinese J. Polym. Sci. 2024, 42, 1341–1352

Cheng-Jiang Lin, Jun-Jun Wang, Yuan Jiang, et al. Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect[J]. Chinese Journal of Polymer Science, 2024, 42(9): 1341-1352.
Lin, C. J.; Wang, J. J.; Jiang, Y.; Chen, S. L.; Li, H. F.; Zhao, W. H.; Huang, Q. R.; Rong, C. R.; Duan, X. Z. Structural properties of ions and polyelectrolytes in aqueous solutions under external electric fields: the sign effect. Chinese J. Polym. Sci. 2024, 42, 1341–1352 DOI： 10.1007/s10118-024-3105-9.

Cheng-Jiang Lin, Jun-Jun Wang, Yuan Jiang, et al. Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect[J]. Chinese Journal of Polymer Science, 2024, 42(9): 1341-1352. DOI： 10.1007/s10118-024-3105-9.

摘要

We utilize molecular dynamics simulations to investigate the microstructures of ions and polyelectrolytes in aqueous solutions under external electric fields. Our simulations illustrate structural variations in ionic solutions caused by reversing the charge sign of ions

and elucidate differences in structures between anionic and cationic polyelectrolytes under external electric fields.

Abstract

We utilize molecular dynamics simulations to investigate the microst

ructures of ions and polyelectrolytes in aqueous solutions under external electric fields. By focusing on the multi-body interactions between ionic components and H

O molecules

as well as their responses to the external electric fields

we clarify several nontrivial molecular features of the ionic and polyelectrolyte solutions

such as the solvations of cations and anions

clustering of the ions

and dispersions/aggregations of polyelectrolyte chains

as well as the corresponding responses of H

O molecules in these contexts. Our simulations illustrate the variations in structures of ionic solutions caused by reversing the charge sign of the ions

and elucidate the disparity in structures between anionic and cationic polyelectrolyte solutions in the presence of the external electric fields. This work clarifies the mechanism for the alternations in complex multi-body interactions in aqueous solutions caused by the application electric field

which can contribute to the fundamental understanding of the physical and chemical natures of ion-containing and charged polymeric systems.

关键词

Keywords

references

Muthukumar, M. Physics of charged macromolecules synthetic and biological systems . Cambridge University Press, 2023 ..

Zhang, Z.; Chen, Q.; Colby, R. H. Dynamics of associative polymers. Soft Matter 2018 , 14 , 2961−2977..

Dobrynin, A. V.; Rubinstein, M. Theory of polyelectrolytes in solutions and at surfaces. Prog. Polym. Sci. 2005 , 30 , 1049−1118..

Dobrynin, A. V. Theory and simulations of charged polymers: from solution properties to polymeric nanomaterials. Curr. Opin. Colloid Interface Sci. 2008 , 13 , 376−388..

Sing, C. E.; Zwanikken, J. W.; Olvera de la C ruz, M. Electrostatic control of block copolymer morphology. Nat. Mater. 2014 , 13 , 694−698..

Shen, K.; Wang, Z. G. Electrostatic correlations and the polyelectrolyte self energy. J. Chem. Phys. 2017 , 146 , 084901..

Friedowitz, S.; Salehi, A.; Larson, R. G.; Qin, J. Role of electrostatic correlations in polyelectrolyte charge association. J. Chem. Phys. 2018 , 149 , 163335..

Brown, J. R.; Seo, Y.; Hall, L. M. Ion correlation effects in salt-doped block copolymers. Phys. Rev. Lett. 2018 , 120 , 127801..

Hao, Q. H.; Xia, G.; Miao, B.; Tan, H. G.; Niu, X. H.; Liu, L. Y. Morphological response of a spherical polyelectrolyte brush to solvent quality and electrostatic interaction strength. Macromolecules 2018 , 51 , 8513−8521..

Liu, L.; Wang, F.; Liu, X.; Guo, L.; Gao, X.; Tan, H. Self-assembly of amphiphilic polyelectrolytes in trivalent salt solution. Phys. Chem. Chem. Phys. 2023 , 25 , 10042−10053..

Fong, K. D.; Self, J.; McCloskey, B. D.; Persson, K. A. Ion correlations and their impact on transport in polymer-based electrolytes. Macromolecules 2021 , 54 , 2575−2591..

Debye, P. Polar molecules . Chemical Catalog Co., New York, 1929 ..

Wang, Z. G. Effects of ion solvation on the miscibility of binary polymer blends. J. Phys. Chem. B 2008 , 112 , 16205−16213..

Levy, A.; Andelman, D.; Orland, H. Dielectric constant of ionic solutions: a field-theory approach. Phys. Rev. Lett. 2012 , 108 , 227801..

Gong, H.; Freed, K. F. Langevin-Debye model for nonlinear electrostatic screening of solvated ions. Phys. Rev. Lett. 2009 , 102 , 057603..

Duan, X.; Nakamura, I. A new lattice Monte Carlo simulation for dielectric saturation in ion-containing liquids. Soft Matter 2015 , 11 , 3566−3571..

Onsager, L. Electric moments of molecules in liquids. J. Am. Chem. Soc. 1936 , 58 , 1486−1493..

Liang, J.; Wei, H.; Yu, K.; Lin, C.; Li, H.; Ding, M.; Duan, X. Structure and dynamics of ions in dipolar solvents: a coarse-grained simulation study. Soft Matter 2021 , 17 , 6305−6314..

Booth, F. The dielectric constant of water and the saturation effect. J. Chem. Phys. 1951 , 19 , 391−394..

Daniels, I. N.; Wang, Z.; Laird, B. B. Dielectric properties of organic solvents in an electric field. J. Phys. Chem. C 2017 , 121 , 1025−1031..

Rezaei, M.; Mitterwallner, B. G.; Loche, P.; Uematsu, Y.; Netz, R. R.; Bonthuis, D. J. Interfacial, electroviscous, and nonlinear dielectric effects on electrokinetics at highly charged surfaces. J. Phys. Chem. B 2021 , 125 , 4767−4778..

Huo, H.; Zhao, W.; Duan, X.; Sun, Z. Y. Control of d iblock copolyelectrolyte morphology through electric field application. Macromolecules 2023 , 56 , 1065−1076..

Herrera, S. E.; Agazzi, M. L.; Apuzzo, E.; Cortez, M. L.; Marmisolle, W. A.; Tagliazucchi, M.; Azzaroni, O. Polyelectrolyte-multivalent molecule complexes: physicochemical properties and applications. Soft Matter 2023 , 19 , 2013−2041..

Fang, Y. N.; Rumyantsev, A. M.; Neitzel, A. E.; Liang, H.; Heller, W. T.; Nealey, P. F.; Tirrell, M. V.; de Pablo, J. J. Scattering evidence of positional charge correlations in polyelectrolyte complexes. Proc. Natl. Acad. Sci. U.S.A. 2023 , 120 , e2302151120..

Ylitalo, A. S.; Balzer, C.; Zhang, P.; Wang, Z. G. Electrostatic correlations and temperature-dependent dielectric constant can model LCST in polyelectrolyte complex coacervation. Macromolecules 2021 , 54 , 11326−11337..

Chen, S.; Zhang, P.; Wang, Z. G. Complexation between oppositely charged polyelectrolytes in dilute solution: effects of charge asymmetry. Macromolecules 2022 , 55 , 3898−3909..

Zhang, P.; Wang, Z. G. Supernatant phase in polyelectrolyte complex coacervation: cluster formation, binodal, and nucleation. Macromolecules 2022 , 55 , 3910−3923..

Wang, L.; Wang, Z.; Jiang, R.; Yin, Y.; Li, B. Conformation transitions of a single polyelectrolyte chain in a poor solvent: a replica-exchange lattice Monte-Carlo study. Soft Matter 2017 , 13 , 2216−2227..

Zhu, Y. L.; Lu, Z. Y.; Milano, G.; Shi, A. C.; Sun, Z. Y. Hybrid particle-field molecular dynamics simulation for polyelectrolyte systems. Phys. Chem. Chem. Phys. 2016 , 18 , 9799−9808..

Wang, R.; Ginzburg, V. V.; Jiang, J.; Wang, Z. G. Adsorption of a polyelectrolyte chain at dielectric surfaces: effects of surface charge distribution and relative dielectric permittivity. Macromolecules 2023 , 56 , 7653−7662..

Chen, X.; Chen, E. Q.; Shi, A. C.; Yang, S. Multiphase coacervates driven by electrostatic correlations. ACS Macro Lett. 2021 , 10 , 1041−1047..

Yang, Z.; Wu, J.; Li, K.; Zhou, X. ; Lu, D.; Zhang, L. Sliding dynamics of a small charged ring chain on the diblock polyelectrolyte in poly[2 ] catenane in the presence of counterions. J. Phys. Chem. B 2023 , 127 , 10189−10200..

Han, Y.; Zhao, X.; Liu, Y.; Li, Y.; Chen, Q. Structure and phase behavior of poly(acrylic acid)-ferric ion complex aqueous solutions. Soft Matter 2020 , 16 , 10750−10758..

Wu, S.; Yang, H.; Chen, Q. Improving stretchability of associative polymers through tuning density of the secondary interactions. J. Rheol. 2023 , 67 , 293−304..

Duan, X.; Shi, A. C.; An, L. Formation of ionomer microparticles via polyelectrolyte complexation. Macromolecules 2021 , 54 , 9053−9062..

Li, B.; Duan, X.; Cheng, D.; Chen, X.; Gao, Z.; Ren, W.; Shao, K.; Zang, H. Controllable transition metal-directed assembly of [Mo 2 O 2 S 2 ] 2+ building blocks into smart molecular humidity-responsive actuators. J. Am. Chem. Soc. 2023 , 145 , 2243−2251..

Liu, B.; Hu, B.; Du, J.; Cheng, D.; Zang, H.; Ge, X.; Tan, H.; Wang, Y.; Duan, X.; Jin, Z.; Zhang, W.; Li, Y.; Su, Z. Precise molecular-level modification of nafion with bismuth oxide clusters for high-performance proton-exchange membranes. Angew. Chem. Int. Ed. 2021 , 60 , 6076−6085..

Yao, L.; Lin, C.; Duan, X.; Ming, X.; Chen, Z.; Zhu, H.; Zhu, S.; Zhang, Q. Autonomous underwater adhesion driven by water-induced interfacial rearrangement. Nat. Commun. 2023 , 14 , 6563..

Chen, L.; Zhao, C.; Duan, X.; Zhou, J.; Liu, M. Finely tuning the lower critical solution temperature of ionogels by regulating the polarity of polymer networks and ionic liquids. CCS Chem. 2022 , 4 , 1386−1396..

Shen, X.; Zhang, Y.; He, H.; Yi, C.; Dong, W.; Ye, S.; Zheng, D.; Tao, J.; Wu, Q.; Duan, X.; Nie, Z. Electrostatic adsorption behaviors of charged polymer-tethered nanoparticles on oppositely charged surfaces. Macromol. Rapid Commun. 2022 , 43 , 2200171..

Zhang, Y.; Yi, C.; Dong, W.; Zheng, D.; Yang, Y.; Li, W.; Duan, X.; Yang, D.; Nie, Z. Single copolymer chain-templated synthesis of ultrasmall symmetric and asymmetric silica-based nanoparticles. Adv. Funct. Mater. 2022 , 32 , 2112742..

Zhang, Q.; He, X. H. Phase separation of polymer blends induced by an external static electric field. Chinese J. Polym. Sci. 2023 , 41 , 972−980..

Zhang, Q.; Xu, R.; Kan, D.; He, X. Molecular dynamics simulation of electric-field-induced self-assembly of diblock copolymers. J. Chem. Phys. 2016 , 144 , 234901..

Balzer, C.; Frischknecht, A. L. Explicit polarization in Coarse-Grained simulations of ionomer melts. Macromolecules 2022 , 55 , 9980−9989..

Zhu, Z.; Duan, X.; Li, Q.; Wu, R.; Wang, Y.; Li, B. Low-noise nanopore enables in-situ and label-free tracking of a trigger-induced DNA molecular machine at the single-molecular level. J. Am. Chem. Soc. 2020 , 142 , 4481−4492..

Wang, Z.; Liang, S.; Yang, Y.; Liu, Z.; Duan, X.; Li, X.; Liu, T.; Zang, H. Complex phase transitions and phase engineering in the aqueous solution of an isopolyoxometalate cluster. Nat. Commun. 2023 , 14 , 2767..

Wilson, C. T. R. Condensation of water vapour in the presence of dust-free air and other gases. Philos. Trans. R. Soc. Lond. A 1897 , 189 , 265−307..

Loeb, L. B.; Kip, A. F.; Einarsson, A. W. On the nature of ionic sign preference in C. T. R. Wilson Cloud Chamber Condensation Experiments. J. Chem. Phys. 1938 , 6 , 264..

Oh, K. J.; Gao, G. T.; Zeng, X. C. Nucleation of water and methanol droplets on cations and anions: the sign preference. Phys. Rev. Lett. 2001 , 86 , 5080−5083..

Russell, K. C. Nucleation on gaseous ions. J. Chem. Phys. 1969 , 50 , 1809..

Talanquer, V.; Oxtoby, D. W. Nucleation in molecular and dipolar fluids: interaction site model. J. Chem. Phys. 1995 , 103 , 3686−3695..

Kusaka, I.; Wang, Z. G.; Seinfeld, J. H. Ion-induced nucleation: a density functional approach. J. Chem. Phys. 1995 , 102 , 913−924..

Kusaka, I.; Wang, Z. G.; Seinfeld, J. H. Ion-induced nucleation. II. Polarizable multipolar molecules. J. Chem. Phys. 1995 , 103 , 8993−9009..

Lin, C.; Wei, H.; Li, H.; Duan, X. Structures of cationic and anionic polyelectrolytes in aqueous solutions: the sign effect. Soft Matter 2022 , 18 , 1603−1616..

Price, D. J.; Brooks, C. L. A modified TIP3P water potential for simulation with Ewald summation. J. Chem. Phys. 2004 , 121 , 10096−10103..

A. D. MacKerell, J.; Bashford, D.; Bellott, M.; R. L. Dunbrack, J.; Evanseck, J. D.; Field, M. J.; Fischer, S.; Gao, J.; Guo, H.; Ha, S.; Joseph-McCarthy, D.; Kuchnir, L.; Kuczera, K.; Lau, F. T. K.; Mattos, C.; Michnick, S.; Ngo, T.; Nguyen, D. T.; Prodhom, B.; W. E. Reiher, I.; Roux, B.; Schlenkrich, M.; Smith, J. C.; Stote, R.; Straub, J.; Watanabe, M.; Wio´rkiewicz-Kuczera, J.; Yin, D.; Karplus, M. All-Atom Empirical Potential for Molecular Modeling and Dynamics Studies of Proteins. J. Phys. Chem. B 1998 , 102 , 3586−3616..

Jorgensen, W. L.; Chandrasekhar, J.; Madura, J. D.; Impey, R. W.; Klein, M. L. Comparison of simple po tential functions for simulating liquid water. J. Chem. Phys. 1983 , 79 , 926−935..

Dang, L. X. Mechanism and thermodynamics of ion selectivity in aqueous solutions of 18-crown-6 ether a molecular dynamics study. J. Am. Chem. Soc. 1995 , 117 , 6954−6960..

Koneshan, S.; Rasaiah, J. C.; Lynden-Bell, R. M.; Lee, S. H. Solvent structure, dynamics, and ion mobility in aqueous solutions at 25 °C. J. Phys. Chem. B 1998 , 102 , 4193−4204..

Dang, L. X. Development of nonadditive intermolecular potentials using molecular dynamics: solvation of Li + and F − ions in polarizable water. J. Chem. Phys. 1992 , 96 , 6970−6977..

Dang, L. X.; Smith, D. E. Molecular dynamics simulations of aqueous ionic clusters using polarizable water. J. Chem. Phys. 1993 , 99 , 6950−6956..

Dang, L. X.; Garrett, B. C. Photoelectron spectra of the hydrated iodine anion from molecular dynamics simulations. J. Chem. Phys. 1993 , 99 , 2972.

Smith, D. E.; Dang, L. X. Computer simulations of NaCl association in polarizable water. J. Chem. Phys. 1994 , 100 , 3757.

Nakamura, I.; Shi, A. C.; Wang, Z. G. Ion solvation in liquid mixtures: effects of solvent reorganization. Phys. Rev. Lett. 2012 , 109 , 257802..

Shock, C. J.; Stevens, M. J.; Frischknecht, A. L.; Nakamura, I. Solvation energy of ions in a stockmayer fluid. J. Phys. Chem. B 2020 , 124 , 4598−4604..

Hall, L. M.; Stevens, M. J.; Frischknecht, A. L. Dynamics of model lonomer melts of various architectures. Macromolecules 2012 , 45 , 8097−8108..

Frenkel, D.; Smit, B. Understanding molecular simulation: from algorithms to applications . Academic, New York, 1996 ..

Darden, T.; York, D.; Pedersen, L. Particle mesh Ewald: An N·log(N) method for Ewald sums in large systems. J. Chem. Phys. 1993 , 98 , 10089.

Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 1995 , 117 , 1−19..

Nishida, K.; Kaji, K.; Kanaya, T. High concentration crossovers of polyelectrolyte solutions. J. Chem. Phys. 2001 , 114 , 8671−8677..

Hejazi, S.; Pahlavanzadeh, H.; Elliott, J. A. W. Thermodynamic investigation of the effect of electric field on solid-liquid equilibrium. J. Phys. Chem. B 2021 , 125 , 1271−1281..

Agrawal, A.; Douglas, J. F.; Tirrell, M.; Karim, A. Manipulation of coacervate droplets with an electric field. Proc. Natl. Acad. Sci. U.S.A. 2022 , 119 , e2203483119..

Colla, T.; Mohanty, P. S.; Nojd, S.; Bialik, E.; Riede, A.; Schurtenberger, P.; Likos, C. N. Self-assembly of ionic microgels driven by an alternating electric field: theory, simulations, and experiments. ACS Nano 2018 , 12 , 4321−4337..

Neumann, M. Dipole moment fluctuation formulas in computer simulations of polar systems. Mol. Phys. 1983 , 50 , 841−858..

Li, Y.; Chang, C.; Zhu, Z.; Sun, L.; Fan, C. Terahertz wave enhances permeability of the voltage-gated calcium channel. J. Am. Chem. Soc. 2021 , 143 , 4311−4318..

Ghalgaoui, A.; Fingerhut, B. P.; Reimann, K.; Elsaesser, T.; Woerner, M. Terahertz polaron oscillations of electrons solvated in liquid water. Phys. Rev. Lett. 2021 , 126 , 097401..

Views

282

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Multicomponent Polymerization of Alkynes, Amines, and Benzaldehyde toward Main-chain Charged Aggregation-induced Emission Polyelectrolytes

Star-shaped Block Copolymers of Poly-2-alkyl-5,6-dihydrooxazines: Synthesis, Conformational Characteristics, Thermoresponsiveness and Complexation with Curcumin

Sliding Dynamics of Ring Chain on a Rod-Coil Block Copolymer in Rotaxane

Molecularly Engineered Polyimide Films with Switchable Cavitation for Bidirectional Passive Thermal Regulation

Tunable Circularly Polarized Luminescence of Helical Poly(phenylacetylene)s via Side-chain-to-Backbone Förster Resonance Energy Transfer

Related Author

Ben-Zhong Tang

An-Jun Qin

Bo Song

Qiu-Shuo Zhang

Nina D. Kozina

Alexander P. Filippov

Tatyana U. Kirila

Serafim V. Rodchenko

Related Institution

Guangdong Basic Research Center of Excellence for Aggregate Science, School of Science and Engineering, The Chinese University of Hong Kong (Shenzhen), Longgang

State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology

Branch of Petersburg Nuclear Physics Institute named by B.P. Konstantinov of National Research Centre «Kurchatov Institute»-Institute of Macromolecular Compounds, Saint Petersburg

Ningbo Institute of Northwestern Polytechnical University

Department of Physics, Ningbo University

⁰