RESUMO
Supramolecular host-guest chemistry bridging the adjustable amphiphilicity and macromolecular self-assembly is well advanced in aqueous media. However, the interfacial self-assembled behaviors have not been further exploited. Herein, we designed a ß-cyclodextrin-grafted alginate/azobenzene-functionalized dodecyl (Alg-ß-CD/AzoC12) supra-amphiphilic system that possessed tunable amphiphilicity by host-guest interfacial self-assembly. Especially, supra-amphiphilic aggregates could be utilized as highly efficient soft colloidal emulsifiers for stabilizing water-in-oil-water (W/O/W) Pickering emulsions due to the excellent interfacial activity. Meanwhile, the assembled particle structures could be modulated by adjusting the oil-water ratio, resulting from the tunable aggregation behavior of supra-amphiphilic macromolecules. Additionally, the interfacial adsorption films could be partially destroyed/reconstructed upon ultraviolet/visible irradiation due to the stimuli-altering balance of amphiphilicity of Alg-ß-CD/AzoC12 polymers, further constructing the stimulus-responsive Pickering emulsions. Therefore, the supramolecular interfacial self-assembly-mediated approach not only technologically advances the continued development of creative templates to construct multifunctional soft materials with anisotropic structures but also serves as a creative bridge between supramolecular host-guest chemistry, colloidal interface science, and soft material technology.
RESUMO
Soft emulsifiers with relatively suitable structural controllability are necessarily required for the preparation of multifunctional Pickering emulsions. Herein, a ß-cyclodextrin-grafted alginate/azobenzene-functionalized dodecyl (Alg-ß-CD/AzoC. 12) polymeric supra-amphiphile was designed based on the host-guest interfacial self-assembly. As compared with Alg-ß-CD amphiphilic polymers, the interfacial tension of Alg-ß-CD/AzoC12 supra-amphiphilic assemblies reduced from 29.57 mN/m to 0.18 mN/m, indicating the great amphiphilicity derived from Alg-ß-CD/AzoC12 supra-amphiphilic assemblies. With the increase of pH, the interfacial microstructures transformed from flocculated structures, spherical structures into deformed structures. Especially, the spherical microstructures with the highest interfacial viscoelasticity and thickness demonstrated the highest emulsifying efficiency due to the steric hindrance mechanism. Moreover, the interfacial elastic modulus of adsorbed layers exhibited ~4 times of that upon the ultraviolet illumination. These results disclosed that the interfacial microstructures could be readily regulated by the tunable amphiphilicity of Alg-ß-CD/AzoC12 assemblies, which would be useful for the applications of Pickering emulsions in numerous fields.