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

Abstract 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, Γ 0 , validate an electrostatic CR model consisting of adsorption and partial neutralization of counterions at a charged interface.