Electrochemical assessments of droplet contents in microfluidic channels. Application to the titration of heterogeneous droplets.

Series of aqueous droplets containing redox species were generated on-demand in a microfluidic channel and detected downstream by an electrochemical cell. Depending on the cell geometry, amperometric detections were performed to simultaneously determine the velocity, volume and content of circulating droplets in oil. Volumes and velocities were estimated from specific transition times on the chronoamperometric responses, while charge were evaluated from current integration. The results showed that the total charge within droplets was controlled by the geometry of the electrochemical cell and droplet velocity, leading to accurate determinations of droplet content under specific operating conditions. An active merging of droplets with titrating solutions was tested for analytical purposes. The results demonstrated that even if the mixing was not complete during detection, the assessment of droplet content was still valid. The performance of electrochemical detection was thus evidenced to determine the content of heterogeneous droplets. This property is pertinent since the design of sophisticated circuits is no longer required to fully homogenize the droplet content before characterization, opening broader perspectives in droplet-based microfluidics.