The prospects of endowing the omnipresent hazardous substances with sensitive, safe, and stable life-like behaviors poses significant for the development of on–off switchable smart materials. Herewith, based on material-structural synergistic design, a multi-level responsiveness smart structures (VBGO) inspired by phospholipid biomolecules is self-assembled through asymmetric swelling and smart supramolecular nano-structures. Due to the outstanding sensitive of fire-warning nano-hybrid of functionalized cyclodextrin-graphene and highly stable substrate of vermiculite, the designed VBGO exhibits the high-sensitively fire alarm time (only 0.17 s) and super-along sustained fire alarm time (up to 249 s). Moreover, the VBGO displays significant increment in thermal stability and film-forming properties. Besides, given the asymmetrical and self-assembled smart structures, the VBGO exhibits the unique fast responses in their surrounding environments like fire, heat, light, humidity, and solvent vapor. Additionally, the on–off switchable mechanisms of fire-warning responsiveness, solvent-/humidity-/light-driven, shape memory and environmental awareness are presented systematically. This work introduces a sensitive, safe, and stable approach to designing multi-level responsive smart materials by modifying fire-warning bioinspired structures.
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