Volatile Chemical Activator Enables Waste-Free Dissipative Supramolecular Assembly.

Dissipative self-assembly in living systems relies on continuous fuel consumption and metabolic removal of waste to maintain non-equilibrium structures. In contrast, most synthetic chemically fueled assemblies accumulate stoichiometric waste, limiting sustainability and repeatability. We report a waste-free, chemically activated dissipative supramolecular gelation strategy enabled by a volatile gaseous activator. Ammonia transiently activates 12-hydroxystearic acid (HSA) through reversible salt formation, converting HSA from a non-assembling OFF state to a self-assembling ON state in polar organic solvents where gelation is otherwise inaccessible. The resulting gels form rapidly, at markedly reduced minimum gelation concentrations, and exhibit tunable lifetimes governed by ammonia dissipation. Multimodal analyses (1H NMR, FTIR, and PXRD) reveal that salt-formation and reinforced hydrogen bonding reorganize lamellar packing, leading to expanded interlayer spacing and cooperative supramolecular assembly. Open systems operate in a true dissipative regime, where continuous ammonia supply maintains the assembled state, while closed systems stabilize the gel through dynamic equilibrium with ammonia. Repeated pulsed ammonia charging and dissipation enable reversible gel-sol cycling without accumulation of persistent chemical waste. This work establishes volatile-activator-driven gelation as a waste-free platform for non-equilibrium supramolecular materials and provides a blueprint for designing chemically activated soft matter systems that more closely emulate the sustainability of biological dissipative assemblies.