Thermo-responsive properties of metallo-supramolecular block copolymer micellar hydrogels

Metallo-supramolecular micellar hydrogels exhibiting thermo-mechanical responsiveness are prepared through the hierarchical assembly of a heterotelechelic associating copolymer. The copolymer consists of a linear thermo-sensitive water-soluble sequence terminated by a short hydrophobic sticker at one end, the other being functionalized by a chelating ligand. As the first level of assembly, the associating copolymer is dissolved in aqueous solution to yield micellar nanostructures, bearing coordinative motifs at the end of the coronal chains. The second level of assembly is achieved when transition metal ions are added to the micellar solutions, resulting in almost instantaneous gelation. The thermo-mechanical response of those materials is investigated in detail by rotational rheometry, showing abrupt changes within the temperature boundaries corresponding to the phase transition of the polymer block located in the micellar corona.