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Unlocking Microdroplet Curious Chemistry through Single Entity ElectrochemistryLynn Elizabeth Krushinski (19831611) 10 October 2024 (has links)
<p dir="ltr">Microdroplets (typically less than 10 μm in radius) have proven to be unique reaction vessels capable of doing the seemingly impossible: drive the chemistry that could have made life possible. While I am not a biochemist here to explain the intricacies of such a claim, I am a measurement scientist who has worked for the past three and half years to develop new methods which can be used to unveil new chemistries in these droplets. Before electrochemists like me entered the microdroplet realm, mass spectrometrists spent years studying droplets at this scale (typically generated with electrospray methods) and have been able to show that these droplets can promote reaction acceleration by several orders of magnitude, spontaneous generation of reactive species such as water and hydroxide radicals as well as hydrogen peroxide, and other curious chemistries. While these studies have changed the way that scientists view microdroplets, they all require the analysis of thousands of droplets in tandem where values are extrapolated back to the average droplet. The robust correlation of chemistry in an individual droplet of a specific size requires the development of new measurement tools capable of accessing single sub-femtoliter droplets, one at a time. Here, I describe the development of new electrochemical measurement tools which have been used to access this curious chemistry at the single droplet level as well as the implications of the findings from the implementation of these tools. First, stochastic electrochemistry, a method where an electrode effectively “fishes” for droplets suspended in an oil phase, will be outlined and it’s use to probe the spontaneous generation of hydrogen peroxide in such droplets will be presented. Afterwards, a method used for the electroanalysis of droplets in air, or aerosols, where an ionic liquid bubble (suspended by a platinum bubble wand) captures droplets to be analyzed at a carbon fiber wire thread through the middle, will be outlined. The use of these two techniques to correlate enzymatic activity in both droplet types, droplets in oil and aerosols, will then reveal that the gas|liquid interface promotes higher turnover rate acceleration for glucose oxidase. Finally, the fabrication and use of a dual-barrel electrode for the analysis of an acoustically levitated droplet will be presented. These three techniques stand to make electrochemistry a pivotal technique for the analysis of the curious chemistry housed within individual microdroplets. In addition to these methods, methods for extending electrochemistry to the next generation of scientists are presented.</p>
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