Tunable Picoliter-Scale Dropicle Formation Using Amphiphilic Microparticles with Patterned Hydrophilic Patches.

Microparticle-templated droplets or dropicles have recently gained interest in the fields of diagnostic immunoassays, single-cell analysis, and digital molecular biology. Amphiphilic particles have been shown to spontaneously capture aqueous droplets within their cavities upon mixing with an immiscible oil phase, where each particle templates a single droplet. Here, an amphiphilic microparticle with four discrete hydrophilic patches embedded at the inner corners of a square-shaped hydrophobic outer ring of the particle (4C particle) is fabricated. Three dimensional computational fluid dynamics simulations predict droplet formation dynamics and differing equilibrium conditions depending on the patterning configuration. Experiments recapitulate equilibrium conditions, enabling tunable dropicle configurations with reproducible volumes down to ≈200 pL templated by the amphiphilic particles. The dropicle configurations depend predominantly on the size of the hydrophilic patches of the 4C particles. This validates that the modeling approach can inform the design of dropicles with varying volumes and numbers per particle, which can be harnessed in new amplified bioassays for greater sensitivity, dynamic range, and statistical confidence.