The gas|liquid interface eclipses the liquid|liquid interface for glucose oxidase rate acceleration in microdroplets.

The curious chemistry observed in microdroplets has captivated chemists in recent years and has led to an investigation into their ability to drive seemingly impossible chemistries. One particularly interesting capability of these microdroplets is their ability to accelerate reactions by several orders of magnitude. While there have been many investigations into which reactions can be accelerated by confinement within microdroplets, no study has directly compared reaction acceleration at the liquid|liquid and gas|liquid interfaces. Here, we confine glucose oxidase, one of life's most important enzymes, to microdroplets and monitor the turnover rate of glucose by the electroactive cofactor, hexacyanoferrate (III). We use stochastic electrochemistry to monitor the collision of single femtoliter water droplets on an ultramicroelectrode. We also develop a measurement modality to robustly quantify reaction rates for femtoliter liquid aerosol droplets, where the majority of the interface is gas|liquid. We demonstrate that the gas|liquid interface accelerates enzyme turnover by over an order of magnitude over the liquid|liquid interface. This is the first apples-to-apples comparison of reaction acceleration at two distinct interfaces that indicates that the gas|liquid interface plays a central role in driving curious chemistry.