Charge Regulation Stabilizes the Formation of Ionic Liquid‐Based Amphiphilic Oligomer Droplet Interface Bilayers

Liu, Zening; Taylor, Graham J.; Luo, Yingdong; Hong, Kunlun; Sacci, Robert L.; Katsaras, John; Carrillo, Jan‐Michael; Doughty, Benjamin L.; Collier, Charles Patrick

doi:10.1002/macp.202400337

Charge Regulation Stabilizes the Formation of Ionic Liquid‐Based Amphiphilic Oligomer Droplet Interface Bilayers

Journal Article · Tue Apr 08 00:00:00 EDT 2025 · Macromolecular Chemistry and Physics

DOI:https://doi.org/10.1002/macp.202400337· OSTI ID:2573238

Liu, Zening ^[1]; Taylor, Graham J. ^[2]; Luo, Yingdong ^[3]; ^[4]; ^[3]; ^[3]; ^[4]; ^[5]; ^[4]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Moleaer Inc., Carson, CA (United States)
Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Graduate Education
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA

Amphiphilic charged oligomers (oligodimethylsiloxane – methylimidazolium cation, ODMS-MIM ⁽⁺⁾), assemble into bilayers using the droplet interface bilayer (DIB) platform, possess similar size and functionality as phospholipid bilayers, but exhibit increased stability. The oligomer ionic headgroups (MIM⁽⁺⁾) are covalently bound to monodisperse, short-chain (n = 13) hydrophobic tails (ODMS). These self-assemble as monolayer brushes at the oil–aqueous interface of water droplets that are influenced by both the charged cationic headgroups, and the nature of the covalently attached tails in the organic phase. Charge regulation (CR) stabilizes the formation of ordered, molecularly close-packed brush phases, which results in highly insulating, stable DIB membranes, with contributions from specific ion-pairing effects, Debye screening, and voltage-dependent electrocompressive stresses. In the oil phase, interactions between hexadecane, a good solvent for ODMS, and the hydrophobic tails result in extended waiting times for bilayer formation compared to phospholipid DIBs, for which hexadecane is a poor solvent. Close agreement between experimental values and predictions for two key parameters, the critical membrane thickness, h_c, and maximal grafted headgroup density, Γ₀, validate an electrostatic CR model consisting of adsorption and partial neutralization of counterions at a charged interface.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2573238

Journal Information:: Macromolecular Chemistry and Physics, Journal Name: Macromolecular Chemistry and Physics Journal Issue: 12 Vol. 226; ISSN 1022-1352; ISSN 1521-3935

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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