Manipulation of Confined Polyelectrolyte Conformations through Dielectric Mismatch

Trung Dac Nguyen, Monica Olvera De La Cruz*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


We demonstrate that a highly charged polyelectrolyte confined in a spherical cavity undergoes reversible transformations between amorphous conformations and a four-fold symmetry morphology as a function of dielectric mismatch between the media inside and outside the cavity. Surface polarization due to dielectric mismatch exhibits an extra "confinement" effect, which is most pronounced within a certain range of the cavity radius and the electrostatic strength between the monomers and counterions and multivalent counterions. For cavities with a charged surface, surface polarization leads to an increased amount of counterions adsorbed in the outer side, further compressing the confined polyelectrolyte into a four-fold symmetry morphology. The equilibrium conformation of the chain is dependent upon several key factors including the relative permittivities of the media inside and outside the cavity, multivalent counterion concentration, cavity radius relative to the chain length, and interface charge density. Our findings offer insights into the effects of dielectric mismatch in packaging and delivery of polyelectrolytes across media with different relative permittivities. Moreover, the reversible transformation of the polyelectrolyte conformations in response to environmental permittivity allows for potential applications in biosensing and medical monitoring.

Original languageEnglish (US)
Pages (from-to)9298-9305
Number of pages8
JournalACS nano
Issue number8
StatePublished - Aug 27 2019


  • coarse-grained simulations
  • confined polyelectrolytes
  • dielectric mismatch
  • four-fold symmetry
  • polarization effects
  • spherical confinement

ASJC Scopus subject areas

  • Engineering(all)
  • Physics and Astronomy(all)
  • Materials Science(all)


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