Reversible fabrication and self-assembly of a gemini supra-amphiphile driven by dynamic covalent bonds

A smart gemini supra-amphiphile behaving with pH/CO2 dual-sensitive hierarchical self-assembly was fabricated under the effect of dynamic covalent bonds. In the presence of an amino-functionalized cation, water-insoluble terephthalaldehyde, and an amphiphilic anion, the benzoic imine bond can initiate the transformation from a single-tailed supra-amphiphile to a gemini supra-amphiphile with increasing pH, followed by the subsequent evolution from micelles to vesicles. Reversible self-assembly and disassembly of the gemini supra-amphiphile can be realized via CO2/N2 treatment, thus inducing the fission and reversion of vesicles. Interestingly, the flexible nature of supra-amphiphiles allows for the hierarchical assembly of vesicles, leading to the formation of aqueous two-phase systems. Multiple responsive supra-amphiphiles have useful applications in the fabrication of smart supra-molecular materials, including self-healing materials, nanocarriers and chemosensors.