pH-Tunable electrokinetic movement of droplets

Abstract

Manipulation and control of droplet motion in an electric field is of interest in biological systems, microfluidics and electrokinetic (EK) separation techniques. In this work, we show that the electrokinetic motion of oil-in-water (O/W) emulsions stabilized by an amphoteric surfactant can be controlled by changing the pH. Amphoteric surfactants carry both positive and negative head groups and change charge under the influence of changing pH, which allows them to impact the surface charge of droplets as a function of pH, and in extension their direction of motion in an electric field. Using a microfluidic system, we evaluate the effect of pH, surfactant concentration and droplet size on the EK velocity of droplets, which is a combination of electrophoresis (EP) and electro-osmotic flow (EOF). We show that by changing the pH from acidic to alkali, the direction of droplet motion in an external electric field changes. The magnitude of the EK velocity at acidic and neutral pH is not significantly altered as a result of the competition of the EP and EOF in the system, which generally have opposite directions. Our results are in good agreement with theoretical predictions for the droplet EP mobility and can thus serve as a verification of the theoretical descriptions. In addition to the pH, the surfactant concentration affects droplet EK velocity, most specifically at pH of 7 which is close to the isoelectric point of the surfactant monomers. At this pH, changing the surfactant concentration changes the direction of droplet motion due the competing effect of the EP and EOF at different surfactant concentrations. By increasing the droplet size, the magnitude of the EK velocity increases because of the larger local ζ-potential of the larger droplets as well as the wall-enhanced effect in the system. The results from this work can be applied to design on-chip droplet separation strategies based on pH variations and are relevant for systems in which pH gradients naturally occur, such as the human body.