Volatile Chemical Activator Enables Waste-Free Dissipative Supramolecular Assembly

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Chemical Engineering

Background:

• Living systems utilize dissipative self-assembly, requiring fuel and waste removal for non-equilibrium structures.
• Synthetic self-assembly often produces stoichiometric waste, hindering sustainability and repeatability.

Purpose of the Study:

• To develop a waste-free, chemically activated dissipative supramolecular gelation strategy.
• To emulate the sustainability of biological dissipative assemblies in synthetic systems.

Main Methods:

• Utilized ammonia as a volatile gaseous activator for 12-hydroxystearic acid (HSA).
• Employed reversible salt formation to switch HSA from a non-assembling to an assembling state.
• Investigated gel properties and assembly mechanisms using 1H NMR, FTIR, and PXRD.

Main Results:

• Achieved rapid gelation in polar organic solvents, previously inaccessible.
• Demonstrated tunable gel lifetimes controlled by ammonia dissipation.
• Observed reorganization of lamellar packing via salt formation and hydrogen bonding, leading to expanded interlayer spacing.
• Showcased reversible gel-sol cycling through pulsed ammonia charging and dissipation without waste accumulation.

Conclusions:

• Established volatile-activator-driven gelation as a sustainable, waste-free platform for non-equilibrium supramolecular materials.
• Provided a blueprint for designing chemically activated soft matter systems inspired by biological dissipative assemblies.