Supramolecular self-assembly between an amino acid-based surfactant and a sulfonatocalixarene driven by electrostatic interactions

•An anionic calixarene associates with a cationic amino acid-based surfactant to form supramolecular aggregates.•Experimental evidence shows the formation of mixed micelles, tubular structures and vesicles.•Aggregate structure is controlled by the calixarene/surfactant mixing ratio.•Results are interpreted in terms of electrostatic complexation and packing effects.

Complex self-assembled structures can be built up in aqueous media by making use of non-covalent interactions between small organic molecules and conventional amphiphiles. The macrocycle p-sulfonatocalix[4]arene (SC4) is a known receptor for organic ammonium cations in aqueous solution, showing strong binding ability for those guests and selectivity for several amino acids. Previous studies have shown that this type of water-soluble calixarenes are able to modify the aggregation behavior of surfactants. Here, we explore the interactions and morphologies present in mixtures of SC4 and a cationic serine-based surfactant, resorting to surface tension, light microscopy, cryo-scanning electron microscopy and nuclear magnetic resonance studies. Complexation of the amino acid-based surfactant by the calixarene leads initially to mixed micelle formation and a significant lowering of the critical micelle concentration with respect to the neat surfactant even for very low content of SC4 (up to 1.4 mol%). Interestingly, as the SC4 fraction in the system is gradually increased (about 2–6 mol%), highly flexible tubular structures and vesicles are assembled. The observed self-assembly is rationalized in terms of electrostatic complexation between the two co-solutes and the preferred packing of the supramolecular complexes formed.

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