CO₂ and Temperature Control over Nanoaggregates in Surfactant-Free Microemulsion

Smart microemulsions (MEs) recently have attracted significant interests. However, MEs, especially surfactant-free MEs (SFMEs) that respond to more than one stimulus, are rarely reported to date. Here, we reported the first example of dual-responsive SFME in which a CO₂-sensitive hydroxyethylamine was used as an amphisolvent. This SFME was investigated utilizing ternary phase diagram, dynamic light scattering, and UV-visible spectrum techniques. It was found that three hydroxyethylamines could stabilize the octanol-water mixture to form transparent and isotropic SFMEs including nanoaggregates-rich pre-ouzo zone, regardless of the number of the hydroxyl group. Among them, 2-(dimethyl amino) ethanol (DMEA)-based SFME possesses the largest single-phase region and most sensitive to CO₂ and the changes in temperature. With bubbling of CO₂/N₂ or decreasing/increasing temperature, both the single-phase region and pre-ouzo zone reversibly shrink and expand, as well as with breathing. However, CO₂/N₂-induced change is more significant than that induced by temperature. The former is mainly ascribed to the reversible protonation and deprotonation of DMEA, while the latter is generally interpreted as the effects of temperature on hydrogen bond interaction. Note that CO₂ leads to a thorough demusification from Winsor IV ME to oil-rich and water-rich two phases without nanoaggregates, while cooling only causes to a particular phase separation, producing two new MEs phases, not typical Winsor I or II MEs. Such a unique dual-responsive SFME can not only be applied in the remediation of contaminated soil, drug delivery, and nanoparticles preparation but also opens a new door to switchable emulsion.