Laminar Flow Infrared Spectroelectrochemistry

In this work, we advance lab-on-chip electrochemistry and spectroscopy by combining these capabilities onto a single platform, thereby achieving mid-infrared spectroelectrochemistry (SEC) for the first time. The key feature of this technique is the use of deterministic laminar flow patterns to precisely transport a reacted solution from upstream electrodes to a downstream spectral detection region. Laminar flow spectroelectrochemistry (LF-SEC) is therefore a completely new approach, which derives its distinction and advantage over traditional SEC by physically separating electrode and attenuated total reflection (ATR) elements. As such, these functional elements retain optimal properties, such as inert, highly conductive electrodes and a bare ATR element for sensitive Fourier transform infrared (FTIR) spectroscopy. By combining ATR-FTIR with a scanning aperture system, LF-SEC provides the additional advantage of spectroscopically monitoring reactions at individual electrodes. The LF-SEC system design is first optimized through a series of targeted experiments using a ferricyanide/ferrocyanide redox pair to validate electrochemical functionality, undertake spectroscopic calibration, optimize experimental parameters, and finally validate the quantitative relationship between FTIR results and the reaction rate under galvanostatic control. After optimization, we demonstrate the technique by monitoring the oxidation of the therapeutic compound ascorbic acid (vitamin C) in the presence of biomolecular interference from a molecule with an overlapping oxidation potential. We find that molecular availability causes the reaction to switch between reaction pathways, which we could finely monitor using LF-SEC. This work opens the door to future developments that take advantage of the microfluidic reactor setup, with benefits ranging from portability to high-throughput studies under precise reaction conditions.