Characterizing Theta-Emitter Generation for Use in Microdroplet Reactions.

Theta emitters are useful for generating microdroplets for rapid-mixing reactions. Theta emitters are glass tips containing an internal septum that separates two channels. When used for mixing, the solutions from each channel are sprayed with mixing occurring during electrospray ionization (ESI) with reaction times on the order of microseconds to milliseconds. Theta emitters of increasing size cause the formation of ESI droplets of increasing size, which require longer times for desolvation and increase droplet lifetimes. Droplets with longer lifetimes provide more time for mixing and allow for increased reaction times prior to desolvation. Because theta emitters are typically produced in-house, there is a need to consistently pull tips with a variety of sizes. Herein, we characterize the effect of pull parameters on the generation of distinct-sized theta emitters using a P-1000 tip puller. Of the examined parameters, the velocity value had the largest impact on the channel diameter. This work also compares the effect of pulling parameters between single-channel and theta capillaries to examine how the internal septum in theta capillaries affects tip pulling. We demonstrate the utility of using theta emitters with different sizes for establishing distinct reaction times. Finally, we offer suggestions on producing theta emitters of various sizes while maintaining high repeatability. Through this work, we provide resources to establish a versatile and inexpensive rapid-mixing system for probing biologically relevant systems and performing rapid derivatizations.