Ion Correlation-Driven Hysteretic Adhesion and Repulsion between Opposing Polyelectrolyte Brushes
Abstract: Polyelectrolyte (PE) brushes are widely used in biomaterials and nanotechnology to regulate surface properties and interactions. Here, we apply the electrostatic correlation augmented self-consistent field theory to investigate the interactions between opposing PE brushes in a mixture of 1:1 and 3:1 salt solutions. Our theory predicts hysteretic feature of the normal stress induced by strong ion correlations. In the presence of trivalent ions, the force profile is discontinuous: repulsive in the compression branch and adhesive in the separation branch. The molecular origin of the hysteretic force is the coexistence of two collapsed modes: two separated condensed layer on each surface in the compression and a single bundled condensed layer in the separation. With the systematic inclusion of ion correlations, our theory fully captures the hysteretic force, adhesive separation, jump-in'' andjump-out'' features, and the ``specific ion effect'', all in good agreement with the reported experimental results.
- N. Ayres, Polymer brushes: Applications in biomaterials and nanotechnology, Polym. Chem. 1, 769 (2010).
- S. Ohta, D. Glancy, and W. C. W. Chan, Dna-controlled dynamic colloidal nanoparticle systems for mediating cellular interaction, Science 351, 841 (2016).
- R. Messina, Electrostatics in soft matter, J. Phys. Condens. Matter 21, 113102 (2009).
- M. Muthukumar, Theory of counter-ion condensation on flexible polyelectrolytes: Adsorption mechanism, J. Chem. Phys. 120, 9343 (2004).
- A. Kundagrami and M. Muthukumar, Theory of competitive counterion adsorption on flexible polyelectrolytes: Divalent salts, J. Chem. Phys. 128, 244901 (2008).
- K. Shen and Z.-G. Wang, Electrostatic correlations and the polyelectrolyte self energy, J. Chem. Phys. 146, 084901 (2017).
- K. Shen and Z.-G. Wang, Polyelectrolyte chain structure and solution phase behavior, Macromolecules 51, 1706 (2018).
- C. E. Sing and J. Qin, Bridging field theory and ion pairing in the modeling of polyelectrolytes and complex coacervation, Macromolecules 56, 5941 (2023).
- C. E. Sing, J. W. Zwanikken, and M. O. de la Cruz, Interfacial behavior in polyelectrolyte blends: Hybrid liquid-state integral equation and self-consistent field theory study, Phys. Rev. Lett. 111, 168303 (2013).
- C. E. Sing, J. W. Zwanikken, and M. O. de la Cruz, Electrostatic control of block copolymer morphology, Nat. Mater. 13, 694 (2014).
- A. Jusufi, C. N. Likos, and H. Löwen, Conformations and interactions of star-branched polyelectrolytes, Phys. Rev. Lett. 88, 018301 (2001).
- A. Jusufi, C. N. Likos, and M. Ballauff, Counterion distributions and effective interactions of spherical polyelectrolyte brushes, Colloid Polym. Sci. 282, 910 (2004).
- D. Prusty, A. Gallegos, and J. Wu, Unveiling the role of electrostatic forces on attraction between opposing polyelectrolyte brushes, Langmuir 40, 2064 (2024).
- C. Duan, N. R. Agrawal, and R. Wang, Ion correlation induced non-monotonic height change and microphase separation of polyelectrolyte brushes, arxiv. , 2404.09103 (2024).
- Z.-G. Wang, Fluctuation in electrolyte solutions: The self energy, Phys. Rev. E 81, 021501 (2010).
- N. R. Agrawal and R. Wang, Electrostatic correlation induced ion condensation and charge inversion in multivalent electrolytes, J. Chem. Theory Comput. 18, 6271 (2022a).
- N. R. Agrawal and R. Wang, Self-consistent description of vapor-liquid interface in ionic fluids, Phys. Rev. Lett. 129, 228001 (2022b).
- N. R. Agrawal, C. Duan, and R. Wang, Nature of overcharging and charge inversion in electrical double layers, J. Phys. Chem. B 128, 303 (2024).
- G. H. Fredrickson, The Equilibrium Theory of Inhomogeneous Polymers, International Series of Monographs on Physics (OUP Oxford, 2006).
- T. Yoshizaki, I. Nitta, and H. Yamakawa, Transport coefficients of helical wormlike chains. 4. intrinsic viscosity of the touched-bead model, Macromolecules 21, 165 (1988).
- E. Hirose, Y. Iwamoto, and T. Norisuye, Chain stiffness and excluded-volume effects in sodium poly(styrenesulfonate) solutions at high ionic strength, Macromolecules 32, 8629 (1999).
- R. Wang and Z.-G. Wang, On the theoretical description of weakly charged surfaces, J. Chem. Phys. 142, 104705 (2015).
Paper Prompts
Sign up for free to create and run prompts on this paper using GPT-5.
Top Community Prompts
Collections
Sign up for free to add this paper to one or more collections.