Surface Morphologies and Dynamic Properties of Polyelectrolyte Brushes Induced by Charge Fraction and Cationic Size

Hong-Yan Zhang; Qing-Hai Hao; Ming-Lu Chao; Hong-Ge Tan

doi:10.1007/s10118-026-3776-5

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Surface Morphologies and Dynamic Properties of Polyelectrolyte Brushes Induced by Charge Fraction and Cationic Size

RESEARCH ARTICLE | Updated：2026-09-20

- Surface Morphologies and Dynamic Properties of Polyelectrolyte Brushes Induced by Charge Fraction and Cationic Size
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-15(2026)
- Affiliations：
  
  College of Science, Civil Aviation University of China, Tianjin 300300, China
- Author bio：
  
  qhhao@cauc.edu.cn (Q.H.H.)
  hgtan@cauc.edu.cn (H.G.T.)
- Funds：
- DOI：10.1007/s10118-026-3776-5
  CLC：
- Received：08 May 2026，
  
  Revised：2026-06-04，
  
  Accepted：09 June 2026，
  
  Online First：20 September 2026，
  
  Published：2026-07
- Accepted：
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Zhang, H. Y.; Hao, Q. H.; Chao, M. L.; Tan, H. G. Surface morphologies and dynamic properties of polyelectrolyte brushes induced by charge fraction and cationic size. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3776-5

Hong-Yan Zhang, Qing-Hai Hao, Ming-Lu Chao, et al. Surface Morphologies and Dynamic Properties of Polyelectrolyte Brushes Induced by Charge Fraction and Cationic Size[J/OL]. Chinese Journal of Polymer Science, 2026, 441-15.
Zhang, H. Y.; Hao, Q. H.; Chao, M. L.; Tan, H. G. Surface morphologies and dynamic properties of polyelectrolyte brushes induced by charge fraction and cationic size. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3776-5 DOI：

Hong-Yan Zhang, Qing-Hai Hao, Ming-Lu Chao, et al. Surface Morphologies and Dynamic Properties of Polyelectrolyte Brushes Induced by Charge Fraction and Cationic Size[J/OL]. Chinese Journal of Polymer Science, 2026, 441-15. DOI： 10.1007/s10118-026-3776-5.

摘要

Abstract

Understanding how the charge sequence along polyelectrolyte (PE) chains and the size of multivalent salt ions cooperatively regulates the behavior of polymer brushes is essential for the rational design of smart surfaces; however

a systematic mechanistic picture of their interplay remains elusive. In this study

we employed molecular dynamics simulations to systematically investigate the roles of the chain charge fraction and trivalent ion size in controlling the structural and dynamic properties of PE brushes. A series of intriguing brush-phase structures emerge from the interplay of these two parameters. Depending on the ion size range

the brush height exhibited three distinct responses to variations in charge fraction. Within different charge-fraction regimes

the brush height displays two contrasting responses to changes in ion size

namely monotonic and non-monotonic behavior. In the multi-chain regime

the structure factor increases monotonically with the charge fraction

whereas it shows a nonmonotonic dependence on the salt ion size. The block effect induced by the chain charge fraction and size effect of multivalent ions jointly give rise to a pronounced diversity in single-chain conformations. Furthermore

the diffusion coefficient revealed two distinct types of responses to the salt ion size

depending on the range of the charge fraction. These findings demonstrate that the synergistic interplay between the charge fraction and the trivalent cation size offers a versatile and powerful strategy for tailoring the equilibrium structures and chain dynamics of PE brushes

thereby providing valuable design guidelines for advanced responsive coatings.

关键词

Keywords

references

Yang, Q.; Li, L.; Zhao, F.; Han, H.; Wang, W.; Tian, Y.; Wang, Y.; Ye, Z.; Guo, X. Hollow silica–polyelectrolyte composite nanoparticles for controlled drug delivery. J. Mater. Sci. 2019 , 54 , 2552−2565..

Yu, Y.; de la Cruz, R. A. L.; Kieviet, B. D.; Gojzewski, H.; Pons, A.; Vancso, G. J.; de Beer, S. Pick up, move and release of nanoparticles utilizing co-non-solvency of PNIPAM brushes. Nanoscale 2017 , 9 , 1670−1675..

Yu, Y.; Kieviet, B. D.; Kutnyanszky, E.; Vancso, G. J.; de Beer, S. Cosolvency-induced switching of the adhesion between poly (methyl methacrylate) brushes. ACS Macro Lett. 2015 , 4 , 75−79..

Psarra, E.; König, U.; Ueda, Y.; Bellmann, C.; Janke, A.; Bittrich, E.; Eichhorn, K.-J.; Uhlmann, P. Nanostructured biointerfaces: nanoarchitectonics of thermoresponsive polymer brushes impact protein adsorption and cell adhesion. ACS Appl. Mater. Interfaces 2015 , 7 , 12516−12529..

Sachar, H. S.; Sivasankar, V. S.; Das, S. Electrokinetic energy conversion in nanochannels grafted with pH-responsive polyelectrolyte brushes modelled using augmented strong stretching theory. Soft Matter 2019 , 15 , 5973−5986..

Zhang, T.; Lu, Q.; Zhang, X.; Liu, S.; Ye, Q.; Zhou, F. Fabrication of polyelectrolyte brush-functionalized two-dimensional covalent organic frameworks as additives for aqueous lubricants. Tribol. Int. 2022 , 174 , 107737..

Zhulina, E. B.; Rubinstein, M. Lubrication by polye lectrolyte brushes. Macromolecules 2014 , 47 , 5825−5838..

Kobayashi, M.; Terada, M.; Takahara, A. Polyelectrolyte brushes: a novel stable lubrication system in aqueous conditions. Faraday Discuss. 2012 , 156 , 403..

Li, B.; Yu, B.; Wang, X.-L.; Guo, F.; Zhou, F. Correlation between conformation change of polyelectrolyte brushes and lubrication. Chinese J. Polym. Sci. 2015 , 33 , 163−172..

Liu, G.; Liu, Z.; Li, N.; Wang, X.; Zhou, F.; Liu, W. Hairy polyelectrolyte brushes-grafted thermosensitive microgels as artificial synovial fluid for simultaneous biomimetic lubrication and arthritis treatment. ACS Appl. Mater. Interfaces 2014 , 6 , 20452−20463..

Smook, L. A.; Dahlin, A.; Schroën, K.; de Beer, S. Responsive polyelectrolyte brushes in applications: functions, stimuli, and design considerations. Adv. Mater. 2025 , 37 , e09580..

Sachar, H. S.; Pial, T. H.; Chava, B. S.; Das, S. All-atom molecular dynamics simulations of weak polyionic brushes: influence of charge density on the prop erties of polyelectrolyte chains, brush-supported counterions, and water molecules. Soft Matter 2020 , 16 , 7808−7822..

Mahalik, J. P.; Yang, Y.; Deodhar, C.; Ankner, J. F.; Lokitz, B. S.; Kilbey, S. M. II, Sumpter, B. G.; Kumar, R. Monomer volume fraction profiles in pH responsive planar polyelectrolyte brushes. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54 , 956−964..

Pial, T. H.; Sachar, H. S.; Das, S. Quantification of mono- and multivalent counterion-mediated bridging in polyelectrolyte brushes. Macromolecules 2021 , 54 , 4154−4163..

Ishraaq, R.; Das, S. All-atom molecular dynamics simulations of cationic polyelectrolyte brushes in the presence of halide counterions. Macromolecules 2024 , 57 , 3037−3046..

Xu, X.; Mastropietro, D.; Ruths, M.; Tirrell, M.; Yu, J. Ion-specific effects of divalent ions on the structure of polyelectrolyte brushes. Langmuir 2019 , 35 , 15564−15572..

Smook, L. A.; de Beer, S. Molecular design strategies to enhance the electroresponse of polyelect rolyte brushes: effects of charge fraction and chain length dispersity. Macromolecules 2025 , 58 , 1185−1195..

Yu, J.; Jackson, N. E.; Xu, X.; Brettmann, B. K.; Ruths, M.; de Pablo, J. J.; Tirrell, M. Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes. Sci. Adv. 2017 , 3 , eaao1497..

Gioldasis, C.; Gergidis, L. N.; Vlahos, C. Complexation of a polyelectrolyte brush with oppositely charged AB diblock copolymers: the zipper brushes. Macromol. Theory Simul. 2022 , 31 , 2200011..

Smook, L. A.; de Beer, S. The effect of salt and monomer distribution on the electroresponse of partially charged polyelectrolyte brushes. J. Polym. Sci. 2025 , 63 , 3446−3455..

Prusty, D.; Gallegos, A.; Wu, J. Modeling ionic and sequence effects on the swelling behavior of polyampholyte brushes. Macromolecules 2024 , 57 , 6666−6680..

Duan, C.; Agrawal, N. R.; Wang, R. Electrostatic correlation augmented self-consistent fieldtheory and its application to polyelectrolyte br ushes. Phys. Rev. Lett. 2025 , 134 , 048101..

Yu, J.; Mao, J.; Yuan, G.; Satija, S.; Jiang, Z.; Chen, W.; Tirrell, M. Structure of polyelectrolyte brushes in the presence of multivalent counterions. Macromolecules 2016 , 49 , 5609−5617..

Li, M.; Zhuang, B.; Yu, J. Effects of ion valency on polyelectrolyte brushes: a unified theory. Macromolecules 2022 , 55 , 10450−10456..

Jackson, N. E.; Brettmann, B. K.; Vishwanath, V.; Tirrell, M.; de Pablo, J. J. Comparing solvophobic and multivalent induced collapse in polyelectrolyte brushes. ACS Macro Lett. 2017 , 6 , 155−160..

Kim, Y. C.; Hoang, S.; Winey, K. I.; Composto, R. J. Size-dependent electrostatic adsorption of polymer-grafted gold nanoparticles on polyelectrolyte brushes. ACS Appl. Mater. Interfaces 2024 , 16 , 61083−61095..

Philippova, O. E.; Rumyantsev, A. M.; Kramarenko, E. Y.; Khokhlov, A. R. New type of swelling behavior upon gel ionization: theory vs experiment. Macromolecules 2013 , 46 , 9359−9367..

Tagliabue, A.; Mella, M. The role of counterion size in defining star-shaped polyelectrolytes thermodynamics, conformations, and ion dynamics. J. Polym. Sci. 2025 , 63 , 3005−3022..

Kremer, K.; Grest, G. S. Dynamics of entangled linear polymermelts: A molecular-dynamics simulation. J. Chem. Phys. 1990 , 92 , 5057−5086..

Murat, M.; Grest, G. S. Molecular dynamics study of dendrimer molecules in solvents of varying quality. Macromolecules 1996 , 29 , 1278−1285..

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

Carrillo, J. Y.; Dobrynin, A. V. Polyelectrolytes in salt solutions: molecular dynamics simulations. Macromolecules 2011 , 44 , 5798−5816..

Carrillo, J. Y.; Brown, W. M.; Dobrynin, A. V. Explicit solvent simulations of friction between brush layers of charged and neutral bottle-brush macromolecules. Macromolecules 2012 , 45 , 8880−8891..

Rodríguez-Ropero, F.; van der Vegt, N. F. A. Ionic specific effects on the structure, mechanics and interfacial softness of a polyelectrolyte brush. Faraday Discuss. 2013 , 160 , 297−309..

Safi Samghabadi, F.; Ramezani Bajgiran, S.; Villegas Orellana, M.; Conrad, J. C.; Marciel, A. B. Charge state of weak polyelectrolyte brushes determines salt-dependent swelling and hysteretic behavior. ACS Macro Lett. 2024 , 13 , 1570−1576..

Robertson, H.; Elliott, G. R.; Nelson, A. R. J.; Le Brun, A. P.; Webber, G. B.; Prescott, S. W.; Craig, V. S. J.; Wanless, E. J.;Willott, J. D. Underscreening in concentrated electrolytes: re-entrant swelling in polyelectrolyte brushes. Phys. Chem. Chem. Phys. 2023 , 25 , 24770−24782..

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