Response of ionizable block copolymer assemblies to solvent dielectrics: A molecular dynamics study

Manjula Senanayake; Dipak Aryal; Gary S. Grest; Dvora Perahia

doi:10.1063/5.0174410

Response of ionizable block copolymer assemblies to solvent dielectrics: A molecular dynamics study

Manjula Senanayake
, Dipak Aryal
, Gary S. Grest
, Dvora Perahia

SNS Science Support 1

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Ionizable copolymers assembly in solutions is driven by the formation of ionic clusters. Fast clustering of the ionizable blocks often leads to the formation of far-from equilibrium assemblies that ultimately impact the structure of polymer membranes and affect their many applications. Using large-scale atomistic molecular dynamics simulations, we probe the effects of electrostatics on the formation of ionizable copolymer micelles that dominate their solution structure, with the overarching goal of defining the factors that control the assembly of structured ionizable copolymers. A symmetric pentablock ionizable copolymer, with a randomly sulfonated polystyrene center tethered to polyethylene-r-propylene block, terminated by poly(t-butyl styrene), in solvents of varying dielectric constants from 2 to 20, serves as the model system. We find that independent of the solvents, this polymer forms a core-shell micelle with the ionizable segment segregating to the center of the assembly. The specific block conformation, however, strongly depends on the sulfonation levels and the dielectric constant and the polarity of the solvents.

Original language	English
Article number	194904
Journal	Journal of Chemical Physics
Volume	159
Issue number	19
DOIs	https://doi.org/10.1063/5.0174410
State	Published - Nov 21 2023

Funding

D.P. gratefully acknowledges the support provided by NSF Grant No. DMR-1905407. The authors kindly acknowledge the use of computational resources provided by NSF Grant No. MRI-1725573. This work was made possible in part by advanced computational resources deployed and maintained by Clemson Computing and Information Technology. This research used resources at the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. This work was performed, in part, at the Center for Integrated Nanotechnologies, a U.S. Department of Energy and Office of Basic Energy Sciences user facility. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under Contract Grant No. DE-NA-0003525. The views expressed in the article do not necessarily represent the views of the U.S. DOE or the United States Government. D.P. gratefully acknowledges the support provided by NSF Grant No. DMR-1905407. The authors kindly acknowledge the use of computational resources provided by NSF Grant No. MRI-1725573. This work was made possible in part by advanced computational resources deployed and maintained by Clemson Computing and Information Technology. This research used resources at the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. This work was performed, in part, at the Center for Integrated Nanotechnologies, a U.S. Department of Energy and Office of Basic Energy Sciences user facility. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under Contract Grant No. DE-NA-0003525. The views expressed in the article do not necessarily represent the views of the U.S. DOE or the United States Government.

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10.1063/5.0174410

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title = "Response of ionizable block copolymer assemblies to solvent dielectrics: A molecular dynamics study",

abstract = "Ionizable copolymers assembly in solutions is driven by the formation of ionic clusters. Fast clustering of the ionizable blocks often leads to the formation of far-from equilibrium assemblies that ultimately impact the structure of polymer membranes and affect their many applications. Using large-scale atomistic molecular dynamics simulations, we probe the effects of electrostatics on the formation of ionizable copolymer micelles that dominate their solution structure, with the overarching goal of defining the factors that control the assembly of structured ionizable copolymers. A symmetric pentablock ionizable copolymer, with a randomly sulfonated polystyrene center tethered to polyethylene-r-propylene block, terminated by poly(t-butyl styrene), in solvents of varying dielectric constants from 2 to 20, serves as the model system. We find that independent of the solvents, this polymer forms a core-shell micelle with the ionizable segment segregating to the center of the assembly. The specific block conformation, however, strongly depends on the sulfonation levels and the dielectric constant and the polarity of the solvents.",

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AU - Aryal, Dipak

AU - Grest, Gary S.

AU - Perahia, Dvora

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N2 - Ionizable copolymers assembly in solutions is driven by the formation of ionic clusters. Fast clustering of the ionizable blocks often leads to the formation of far-from equilibrium assemblies that ultimately impact the structure of polymer membranes and affect their many applications. Using large-scale atomistic molecular dynamics simulations, we probe the effects of electrostatics on the formation of ionizable copolymer micelles that dominate their solution structure, with the overarching goal of defining the factors that control the assembly of structured ionizable copolymers. A symmetric pentablock ionizable copolymer, with a randomly sulfonated polystyrene center tethered to polyethylene-r-propylene block, terminated by poly(t-butyl styrene), in solvents of varying dielectric constants from 2 to 20, serves as the model system. We find that independent of the solvents, this polymer forms a core-shell micelle with the ionizable segment segregating to the center of the assembly. The specific block conformation, however, strongly depends on the sulfonation levels and the dielectric constant and the polarity of the solvents.

AB - Ionizable copolymers assembly in solutions is driven by the formation of ionic clusters. Fast clustering of the ionizable blocks often leads to the formation of far-from equilibrium assemblies that ultimately impact the structure of polymer membranes and affect their many applications. Using large-scale atomistic molecular dynamics simulations, we probe the effects of electrostatics on the formation of ionizable copolymer micelles that dominate their solution structure, with the overarching goal of defining the factors that control the assembly of structured ionizable copolymers. A symmetric pentablock ionizable copolymer, with a randomly sulfonated polystyrene center tethered to polyethylene-r-propylene block, terminated by poly(t-butyl styrene), in solvents of varying dielectric constants from 2 to 20, serves as the model system. We find that independent of the solvents, this polymer forms a core-shell micelle with the ionizable segment segregating to the center of the assembly. The specific block conformation, however, strongly depends on the sulfonation levels and the dielectric constant and the polarity of the solvents.

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Response of ionizable block copolymer assemblies to solvent dielectrics: A molecular dynamics study

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