Host–guest driven supramolecular assembly of reversible comb-shaped polymers in aqueous solution

We report an original strategy towards supramolecular assembly of reversible comb-shaped polymers in aqueous solution through β-cyclodextrin–adamantane (β-CD–Ada) host–guest inclusion. Ada-functionalized poly(acrylic acid) grafts were generated by RAFT polymerization mediated by an adamantane-α-functionalized RAFT agent. A β-CD-grafted backbone was obtained by a two-step procedure: alkyne-functionalized backbones were first generated by RAFT polymerization of trimethylsilyl propargyl methacrylate and subsequently converted in a host system by CuAAC with azide-functionalized β-CD. The self-assembly between a β-CD-grafted polymer backbone and Ada-functionalized grafts was highlighted by 1H 2D NOESY NMR in D2O and by DLS. The reversible character of the host–guest association between the complementary macromolecular blocks was demonstrated by DLS through the addition of competing free β-CD.