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Tuning the selective permeability of polydisperse polymer networks

Kim, Won Kyu ; Chudoba, Richard LU orcid ; Milster, Sebastian ; Roa, Rafael ; Kanduč, Matej and Dzubiella, Joachim (2020) In Soft Matter 16(35). p.8144-8154
Abstract

We study the permeability and selectivity ('permselectivity') of model membranes made of polydisperse polymer networks for molecular penetrant transport, using coarse-grained, implicit-solvent computer simulations. In our work, permeability P is determined on the linear-response level using the solution-diffusion model, P = KDin, i.e., by calculating the equilibrium penetrant partition ratio K and penetrant diffusivity Din inside the membrane. We vary two key parameters, namely the network-network interaction, which controls the degree of swelling and collapse of the network, and the network-penetrant interaction, which tunes the selective penetrant uptake and microscopic energy landscape for diffusive transport. We find that the... (More)

We study the permeability and selectivity ('permselectivity') of model membranes made of polydisperse polymer networks for molecular penetrant transport, using coarse-grained, implicit-solvent computer simulations. In our work, permeability P is determined on the linear-response level using the solution-diffusion model, P = KDin, i.e., by calculating the equilibrium penetrant partition ratio K and penetrant diffusivity Din inside the membrane. We vary two key parameters, namely the network-network interaction, which controls the degree of swelling and collapse of the network, and the network-penetrant interaction, which tunes the selective penetrant uptake and microscopic energy landscape for diffusive transport. We find that the partitioning K covers four orders of magnitude and is a non-monotonic function of the parameters, well interpreted by a second-order virial expansion of the free energy of transferring one penetrant from a reservoir into the membrane. Moreover, we find that the penetrant diffusivity Din in the polydisperse networks, in contrast to highly ordered membrane structures, exhibits relatively simple exponential decays. We propose a semi-empirical scaling law for the penetrant diffusion that describes the simulation data for a wide range of densities and interaction parameters. The resulting permeability P turns out to follow the qualitative behavior (including maximization and minimization) of partitioning. However, partitioning and diffusion are typically anti-correlated, yielding large quantitative cancellations, controlled and fine-tuned by the network density and interactions, as rationalized by our scaling laws. We finally demonstrate that even small changes of network-penetrant interactions, e.g., by half a kBT, modify the permselectivity by almost one order of magnitude.

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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Soft Matter
volume
16
issue
35
pages
11 pages
publisher
Royal Society of Chemistry
external identifiers
  • pmid:32935731
  • scopus:85091051786
ISSN
1744-6848
DOI
10.1039/d0sm01083a
language
English
LU publication?
yes
id
6901b5c6-4f53-42bc-9268-9623511a6990
date added to LUP
2020-09-29 12:55:30
date last changed
2024-05-29 19:55:07
@article{6901b5c6-4f53-42bc-9268-9623511a6990,
  abstract     = {{<p>We study the permeability and selectivity ('permselectivity') of model membranes made of polydisperse polymer networks for molecular penetrant transport, using coarse-grained, implicit-solvent computer simulations. In our work, permeability P is determined on the linear-response level using the solution-diffusion model, P = KDin, i.e., by calculating the equilibrium penetrant partition ratio K and penetrant diffusivity Din inside the membrane. We vary two key parameters, namely the network-network interaction, which controls the degree of swelling and collapse of the network, and the network-penetrant interaction, which tunes the selective penetrant uptake and microscopic energy landscape for diffusive transport. We find that the partitioning K covers four orders of magnitude and is a non-monotonic function of the parameters, well interpreted by a second-order virial expansion of the free energy of transferring one penetrant from a reservoir into the membrane. Moreover, we find that the penetrant diffusivity Din in the polydisperse networks, in contrast to highly ordered membrane structures, exhibits relatively simple exponential decays. We propose a semi-empirical scaling law for the penetrant diffusion that describes the simulation data for a wide range of densities and interaction parameters. The resulting permeability P turns out to follow the qualitative behavior (including maximization and minimization) of partitioning. However, partitioning and diffusion are typically anti-correlated, yielding large quantitative cancellations, controlled and fine-tuned by the network density and interactions, as rationalized by our scaling laws. We finally demonstrate that even small changes of network-penetrant interactions, e.g., by half a kBT, modify the permselectivity by almost one order of magnitude.</p>}},
  author       = {{Kim, Won Kyu and Chudoba, Richard and Milster, Sebastian and Roa, Rafael and Kanduč, Matej and Dzubiella, Joachim}},
  issn         = {{1744-6848}},
  language     = {{eng}},
  number       = {{35}},
  pages        = {{8144--8154}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Soft Matter}},
  title        = {{Tuning the selective permeability of polydisperse polymer networks}},
  url          = {{http://dx.doi.org/10.1039/d0sm01083a}},
  doi          = {{10.1039/d0sm01083a}},
  volume       = {{16}},
  year         = {{2020}},
}