Using the pH sensitivity of switchable surfactants to understand the role of the alkyl tail conformation and hydrogen bonding at a molecular level in elucidating emulsion stability

Abstract

HypothesisThe monoalkyl diamine surfactant, N-dodecylpropane-1,3-diamine (DPDA), is expected to exhibit a pH-dependent charge switchability. In response to pH changes, the interfacial self-assembly of DPDA becomes an intermediary constituent that can potentially modify the interfacial interactions and structural assembly of both the oil and water phases. Hence, we hypothesize that as we change the pH, DPDA will respond to it by changing its charge and alkyl tail conformation as well as the conformation of adjacent phases at the molecular level, consequently affecting emulsion formation and stability. A neutral pH, resulting in a mono-cationic dialkyl amine, affects the conformation, driving an ordered self-assembly and stable emulsion. ExperimentsThe pH-sensitivity and interfacial activity of DPDA were evaluated through pH titration and interfacial tension measurements. Subsequently, a molecular-level study of DPDA, as a pH-sensitive switchable surfactant, was performed at the dodecane-water interface using SFG spectroscopy. The interpretation of the vibrational spectra was further reinforced by determining the gauche defects in the interfacial alkyl chain organization and the extent of hydrogen (H) bonding between the interfacial water molecules. FindingsBy adjusting the pH of water, the charge of the adsorbed DPDA molecules, their self-assembly, the organization of interfacial molecules, and ultimately the stability of the emulsion were tuned. At pH 7.0, the SFG spectra of DPDA showed that the interfacial alkyl chains were relatively well-ordered, while water molecules also had stronger H-bonding interactions. As a result, the oil–water emulsion showed improved stability. When water was at a high pH, the water molecules had fewer H-bonding interactions and relatively disordered alkyl chains at the interface, providing desirable conditions for demulsification. These observations were compatible with the observation in bulk emulsion preparation, confirming that alkyl chain packing and water H-bonding interactions at the interface contribute to overall emulsion stability.