Dynamic Fluorescence Visualization of Nonequilibrium Supramolecular Assembly Regulated by a Proton Reservoir

ABSTRACT

Living systems sustain nonequilibrium supramolecular assemblies through continuous energy input and concomitant dissipation, with adenosine triphosphate (ATP) serving as a universal chemical fuel that regulates dynamic processes by coupling hydrolysis to downstream chemical or conformational changes. Biomimetic recreation of this behavior remains challenging because fuel‐mediated regulation in artificial assemblies is typically coupled to building‐block structure, limiting independent control over assembly dynamics and real‐time monitoring. Here we report amphiphile‐based fluorescent assemblies regulated by a time‐programmable proton reservoir, where the fuel‐consuming esterification–hydrolysis cycle is decoupled from the building blocks and controls assembly through programmed acid availability. The amphiphilic building blocks undergo stimulus–responsive assembly with fluorescence color tunable from blue to green, yellow, and white, and quantum yields spanning 1.7%–71.9%. The proton reservoir temporarily holds acid in hydrolysable esterified forms and subsequently regenerates acid over prescribed timescales; by molecular design, the acid‐masking period is tuned from 0 to 250 min and acid regeneration from 10 to 120 min. Coupling this cycle to the fluorescent assembly regulates nonequilibrium organization, enables catalytic nucleophilic reactions, and provides an intrinsic optical signal for visualizing fuel consumption and assembly transformation in real time.