Chemical Programming of Solubilizing, Nonequilibrium Active Droplets.

ConspectusThe multifunctionality and resilience of living systems has inspired an explosion of interest in creating materials with life-like properties. Just as life persists out-of-equilibrium, we too should try to design materials that are thermodynamically unstable but can be harnessed to achieve desirable, adaptive behaviors. Studying minimalistic chemical systems that exhibit relatively simple emergent behaviors, such as motility, communication, or self-organization, can provide insight into fundamental principles which may enable the design of more complex and life-like synthetic materials in the future.Emulsions, which are composed of liquid droplets dispersed in another immiscible fluid phase, have emerged as fascinating chemically minimal materials in which to study nonequilibrium, life-like properties. As covered in this Account, our group has focused on studying oil-in-water emulsions, specifically those which destabilize by solubilization, a process wherein oil is released into the continuous phase over time to create gradients of oil-filled micelles. These chemical gradients can create interfacial tension gradients that lead to droplet self-propulsion as well as mediate communication between neighboring oil droplets. As such, oil-in-water emulsions present an interesting platform for studying active matter. However, despite being chemically minimal with sometimes as few as three chemicals (oil, water, and a surfactant), emulsions present surprising complexity across the molecular to macroscale. Fundamental processes governing their active behavior, such as micelle-mediated interfacial transport, are still not well understood. This complexity is compounded by the challenges of studying systems out-of-equilibrium which typically require new analytical methods and may break our intuition derived from equilibrium thermodynamics.In this Account, we highlight our group's efforts toward developing chemical frameworks for understanding active and interactive oil-in-water emulsions. How do the chemical properties and physical spatial organization of the oil, water, and surfactant combine to yield colloidal-scale active properties? Our group tackles this question by employing systematic studies of active behavior working across the chemical space of oils and surfactants to link molecular structure to active behavior. The Account begins with an introduction to the self-propulsion of single, isolated droplets and how by applying biases, such as with a gravitational field or interfacially adsorbed particles, drop speeds can be manipulated. Next, we illustrate that some droplets can be attractive, as well as self-propulsive/repulsive, which does not fall in line with the current understanding of the impact of oil-filled micelle gradients on interfacial tensions. The mechanisms by which oil-filled micelles influence interfacial tensions of nonequilibrium interfaces is poorly understood and requires deeper molecular understanding. Regardless, we extend our knowledge of droplet motility to design emulsions with nonreciprocal predator-prey interactions and describe the dynamic self-organization that arises from the combination of reciprocal and nonreciprocal interactions between droplets. Finally, we highlight our group's progress toward answering key chemical questions surrounding nonequilibrium processes in emulsions that remain to be answered. We hope that our progress in understanding the chemical principles governing the dynamic nonequilibrium properties of oil-in-water droplets can help inform research in tangential research areas such as cell biology and origins of life.