Single-Molecule Interactions at a Surfactant-Modified H₂ Surface Nanobubble

In schematics and cartoons, the gas-liquid interface is often drawn as solid lines that aid in distinguishing the separation of the two phases. However, on the molecular level, the structure, shape, and size of the gas-liquid interface remain elusive. Furthermore, the interactions of molecules at gas-liquid interfaces must be considered in various contexts, including atmospheric chemical reactions, wettability of surfaces, and numerous other relevant phenomena. Hence, understanding the structure and interactions of molecules at the gas-liquid interface is critical for further improving technologies that operate between the two phases. Electrochemically generated surface nanobubbles provide a stable, reproducible, and high-throughput platform for the generation of a nanoscale gas-liquid boundary. We use total internal reflection fluorescence microscopy to image single-fluorophore labeling of surface nanobubbles in the presence of a surfactant. The accumulation of a surfactant on the nanobubble surface changes the interfacial properties of the gas-liquid interface. The single-molecule approach reveals that the fluorophore adsorption and residence lifetime at the interface is greatly impacted by the charge of the surfactant layer at the bubble surface. We demonstrate that the fluorescence readout is either short- or long-lived depending on the repulsive or attractive environment, respectively, between fluorophores and surfactants. Additionally, we investigated the effect of surfactant chain length and salt type and concentration on the fluorophore lifetime at the nanobubble surface.