Dynamic Duo: Vibrational Sum Frequency Scattering Investigation of pH-Switchable Carboxylic Acid/Carboxylate Surfactants on Nanodroplet Surfaces.

Surfactants containing pH-switchable, carboxylic acid moieties are utilized in a variety of environmental, industrial, and biological applications that require controlled stability of hydrophobic droplets in water. For nanoemulsions, kinetically stable oil droplets in water, surface adsorption of the anionic form of the carboxylic acid surfactant stabilizes the droplet, whereas a dominant surface presence of the neutral form leads to destabilization. Through the use of dynamic light scattering, ζ-potential, and vibrational sum frequency scattering spectroscopy (VSFSS), we investigate this mechanism and the relative surface population of the neutral and charged species as pH is adjusted. We find that the relative population of the two surfactant species at the droplet surface is distinctly different than their bulk equilibrium concentrations. The ζ-potential measurements show that the surface concentration of the charged surfactant stays nearly constant throughout the stabilizing pH range. In contrast, VSFSS shows that the neutral carboxylic acid form increasingly adsorbs to the surface with increased acidity. The spectral features of the headgroup vibrational modes confirm this behavior and go further to reveal additional molecular details of their adsorption. A significant hydrogen-bonding interaction occurs between the headgroups that, along with hydrophobic chain-chain interactions, assists in drawing more carboxylic acid surfactant to the interface. The charged surfactant provides the stabilizing force for these droplets, while the neutral surfactant introduces complexity to the interfacial structure as the pH is lowered. The results are significantly different than what has been found for the planar oil/water studies where stabilization of the interface is not a factor.