Self‐Assembly of Polyrotaxanes Synthesized Via Click Chemistry of Azido‐Endcapped PNIPAAm‐b‐Pluronic F68‐b‐PNIPAAm/γ‐CD with Propargylamine‐Substituted β‐CDs

A kind of γ‐(cyclodextrin) (γ‐CD)‐based polyrotaxane (PR) is synthesized via an aqueous click reaction between propargylamine‐substituted β‐CD and polypseudorotaxanes (PPRs) self‐assembled from azido‐endcapped PNIPAAm‐b‐Pluronic F68‐b‐PNIPAAm with a varying amount of γ‐CD. The evolution of the self assembly, dependent on the preparation process, is observable by X‐ray diffraction (XRD) and DSC analyses. The γ‐CD is able to be included and preferably entrapped on the PNIPAAm blocks, showing a unique loose‐fit aggregate structure after the click reaction. Most γ‐CDs gradually slip over to the middle PPG block of Pluronic F68, giving rise to a characteristic channel‐type crystal structure in the dialy­sis process. In addition, the lower critical solution temperature (LCST) is sharply enhanced due to the coverage of the remaining γ‐CDs hindering the thermally responsive aggregation of the PNIPAAm blocks.