Out-of-equilibrium molecular systems hold great promise as dynamic, reconfigurable matter that executes complex tasks autonomously. However, translating molecular scale dynamics into spatiotemporally controlled phenomena emerging at mesoscopic scale remains a challenge—especially if one aims at a design where the system itself maintains gradients that are required to establish spatial differentiation. Here, we demonstrate how surface tension gradients, facilitated by a linear amphiphile molecule, generate Marangoni flows that coordinate the positioning of amphiphile source and drain droplets floating at air-water interfaces. Importantly, at the same time, this amphiphile leads, via buckling instabilities in lamellar systems of said amphiphile, to the assembly of millimeter long filaments that grow from the source droplets and get absorbed at the drain droplets. Thereby, the Marangoni flows and filament organization together sustain the autonomous positioning of interconnected droplet-filament networks at the mesoscale. Our concepts provide potential for the development of non-equilibrium matter with spatiotemporal programmability.

Self-organization of meso- and macroscale structures is a highly active research field that exploits a wide variety of physicochemical phenomena, including surface tension, Marangoni flow, and (elasto)capillary effects. The release of surface-active compounds generates Marangoni flows that cause repulsion, whereas capillary forces attract floating particles via the Cheerios effect. Typically, the interactions resulting from these effects are nonselective because the gradients involved are uniform. In this work, we unravel the mechanisms involved in the self-organization of amphiphile filaments that connect and attract droplets floating at the air–water interface, and we demonstrate their potential for directional gradient formation and thereby selective interaction. We simulate Marangoni flow patterns resulting from the release and depletion of amphiphile molecules by source and drain droplets, respectively, and we predict that these flow patterns direct the growth of filaments from the source droplets toward specific drain droplets, based on their amphiphile depletion rate. The interaction between such droplets is then investigated experimentally by charting the flow patterns in their surroundings, while the role of filaments in source–drain attraction is studied using microscopy. Based on these observations, we attribute attraction of drain droplets and even solid objects toward the source to elastocapillary effects. Finally, the insights from our simulations and experiments are combined to construct a droplet-based system in which the composition of drain droplets regulates their ability to attract filaments and as a consequence be attracted toward the source. Thereby, we provide a novel method through which directional attraction can be established in synthetic self-organizing systems and advance our understanding of how complexity arises from simple building blocks.

We highlight four different concepts that can be used as a design principe to establish self-organization using chemical reactions as a driving force to sustain gradients: reaction–diffusion, reaction–convection, Marangoni flow and diffusiophoresis.