Computational Insights into a CO₂-Responsive Emulsion Prepared Using the Superamphiphile Assembled by Electrostatic Interactions

The superamphiphiles exhibit broad prospects for fabricating stimuli-responsive emulsions. Because the superamphiphiles are assembled via noncovalent interactions, they have the advantage of fast response and high efficiency. Recently, a series of switchable emulsions using CO2-responsive superamphiphiles have been developed, which extends the applications of CO2-responsive materials in widespread field. However, there is still a lack of fundamental understanding on the switching mechanism related to the assembled structure of superamphiphiles at the oil-water interface. We employed molecular dynamics (MD) simulations to investigate the reversible emulsification/demulsification process of a responsive emulsion system stabilized by a recently developed responsive superamphiphile (BTOA), which consists of oleic acid (OA) and cationic amine (named 1,3-bis(aminopropyl)tetramethyldisiloxane, BT). The simulation results present the morphologies in both the emulsion and demulsification states. It is found that the ionized OA(-) and the protonated BT+ together form an adsorption layer at the oil-water interface. The hydrophobic parts of BT+ are inserted into the adsorption layer, and the two amine groups contact the water phase. This adsorption layer reduces the interfacial tension and stabilizes the emulsion. After the bubbling of CO2, the surfactants were fully protonated to OA and BT2+. Because of the changes in the molecular polarity, OA and BT2+ entered the oil and water phases, respectively, resulting in demulsification. The structural and dynamical properties were analyzed to reveal the different intermolecular interactions that were responsible for the reversible reversibility of the emulsion. The observations are considered to be complementary to experimental studies and are expected to provide deeper insights into studies on developing responsive materials via supramolecular assemblies.