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Surface Polarization Effects on Collapse Transition of Polyelectrolyte Brushes

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Polyelectrolyte brushes(PEBs)are commonly used to modify surface that have attracted great research interest.The dielectric permit-tivity of the grafted surface is typically significantly different from that of solution,which results in surface polarization(SP)effect with a jump of electric field.It is thus important to study how SP alters the PEB's structure and properties.In this work,the SP effects on PEB structure was stud-ied using a statistical thermodynamic theory.The free energy functional to describe SP effect was constructed by using the image-charge method.Meanwhile,the electrostatic potential was solved from a modified Poisson-Boltzmann equation taking the ion solvation effect into con-sideration.In the absence of SP,the thickness of PEB exhibited a continuous collapse transition when decreasing the solvent quality.In the pres-ence of SP,the collapse became a jump-like transition.Free energy analysis showed that the long-range Coulombic interaction dominated the transition because of the enhanced counterion condensation in the presence of SP.The theory provides an effective tool to study SP effect on PEBs,and the results explain the underlying physics in PEB collapse transition.

Surface polarizationPolyelectrolyte brushImage chargeIon solvationPolyelectrolyte collapse transition

Xiao-Fei Xu

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State Key Laboratory of Chemical Engineering and School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China

National Natural Science Foundation of China

21978079

2024

高分子科学(英文版)
中国化学会 中国科学院化学研究所

高分子科学(英文版)

CSTPCD
影响因子:0.721
ISSN:0256-7679
年,卷(期):2024.42(9)