pH drives electron density fluctuations that enhance electric field-induced liquid flow.

Liquid flow along a charged interface is commonly described by classical continuum theory, which represents the electric double layer by uniformly distributed point charges. The electrophoretic mobility of hydrophobic nanodroplets in water doubles in magnitude when the pH is varied from neutral to mildly basic (pH 7 → 11). Classical continuum theory predicts that this increase in mobility is due to an increased surface charge. Here, by combining all-optical measurements of surface charge and molecular structure, as well as electronic structure calculations, we show that surface charge and molecular structure at the nanodroplet surface are identical at neutral and mildly basic pH. We propose that the force that propels the droplets originates from two factors: Negative charge on the droplet surface due to charge transfer from and within water, and anisotropic gradients in the fluctuating polarization induced by the electric field. Both charge density fluctuations couple with the external electric field, and lead to droplet flow. Replacing chloride by hydroxide doubles both the charge conductivity via the Grotthuss mechanism, and the droplet mobility. This general mechanism deeply impacts a plethora of processes in biology, chemistry, and nanotechnology and provides an explanation of how pH influences hydrodynamic phenomena and the limitations of classical continuum theory currently used to rationalize these effects.

Interfacial Inversion, Interference, and IR Absorption in Vibrational Sum Frequency Scattering Experiments.

Molecular interfacial structure greatly determines the properties of nano- and microscale systems. Vibrational sum frequency scattering (SFS) spectroscopy is a unique interface-selective tool to measure the interfacial vibrational spectrum of sub-micron to micron-scale objects dispersed in liquid and solid media. The interfacial structure is extracted from the interfacial susceptibility, a physical property derived from the intensity. Here, we describe the effect of infrared absorption that occurs in a bulk medium that is spectroscopically complex and use the results to investigate the effects of interfacial inversion, interfacial interference, and interfacial interference combined with absorption. We use the same three chemicals to do so, hexadecane oil, water, and a neutral Span80 surfactant. For all cases, the effective surface susceptibility can be retrieved from the intensity. We further find that inverting the phases results in different interfacial structures, even though they are composed of the same three chemicals, and explain this in terms of the different interactions that are necessary to stabilize the drops: steric stabilization for water drops in oil vs. charge stabilization for oil drops in water. Interfacial interference can be used to estimate the surface density of different compounds.

Water Structure at the Hydrophobic Nanodroplet Surface Revealed by Vibrational Sum Frequency Scattering Using Isotopic Dilution.

The water structure at the hydrophobic/water interface is key toward understanding hydrophobicity at the molecular level. Herein, we characterize the hydrogen-bonding network of interfacial water next to sub-micron-sized hydrophobic oil droplets dispersed in water using isotopic dilution vibrational sum frequency scattering (SFS) spectroscopy. The relative intensity of different modes, the frequency shift of the uncoupled O-D spectrum, and a low-frequency shoulder (2395 cm-1) reveal that water forms an overall stronger hydrogen-bonding network next to hydrophobic droplets compared to bulk water and the air/water interface. Half of the spectral width of the oil droplet SFS spectrum is determined by inter- and intramolecular coupling of water molecules. Isotopic dilution also confirms the presence of a broad distribution (ca. 2640-2745 cm-1) of non-water-hydrogen-bonded O-D modes that are red-shifted and broadened compared to similar species at the air/water interface. This band corroborates the presence of charge transfer between water and oil.

On the stability and necessary electrophoretic mobility of bare oil nanodroplets in water.

Hydrophobic oil droplets, particles, and air bubbles can be dispersed in water as kinetically stabilized dispersions. It has been established since the 19th century that such objects harbor a negative electrostatic potential roughly twice larger than the thermal energy. The source of this charge continues to be one of the core observations in relation to hydrophobicity, and its molecular explanation is still debated. What is clear though is that the stabilizing interaction in these systems is understood in terms of electrostatic repulsion via Derjaguin, Landau, Verwey, and Overbeek theory. Recent work [A. P. Carpenter et al., Proc. Natl. Acad. Sci. U. S. A. 116, 9214 (2019)] has added another element into the discussion, reporting the creation of bare near-zero charged droplets of oil in neat water that are stable for several days. Key to the creation of the droplets is a rigorous glassware cleaning procedure. Here, we investigate these conclusions and show that the cleaning procedure of glassware has no influence on the electrophoretic mobility of the droplets and that oil droplets with near-zero charge are unstable. We provide an alternative possible explanation for the observations involving glass surface chemistry.