TY - JOUR
T1 - Manipulation of Confined Polyelectrolyte Conformations through Dielectric Mismatch
AU - Nguyen, Trung Dac
AU - Olvera De La Cruz, Monica
N1 - Funding Information:
The research was supported by the Sherman Fairchild Foundation and by the Center for Computation and Theory of Soft Materials. We thank Michael Engel (FAU Erlangen-Nuremberg) for sharing the code used to generate the diffraction patterns.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/8/27
Y1 - 2019/8/27
N2 - 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.
AB - 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.
KW - coarse-grained simulations
KW - confined polyelectrolytes
KW - dielectric mismatch
KW - four-fold symmetry
KW - polarization effects
KW - spherical confinement
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U2 - 10.1021/acsnano.9b03900
DO - 10.1021/acsnano.9b03900
M3 - Article
C2 - 31404496
AN - SCOPUS:85071691013
VL - 13
SP - 9298
EP - 9305
JO - ACS Nano
JF - ACS Nano
SN - 1936-0851
IS - 8
ER -