Supramolecular ABC Miktoarm Star Terpolymer Based on Host-Guest Inclusion Complexation

A facile strategy for the construction of supramolecular star-shaped ABC terpolymer was proposed and realized via the molecular recognition between beta-cyclodextrin- (beta-CD-) based host and adamantane-(AD-)modified guest. In the first step, beta-CD with two different functional groups was prepared, which was further used to construct a diblock copolymer host via click reaction with alkynyl-poly(ethylene glycol) (alkynyl-PEG) and atom transfer radical polymerization (ATRP) of dimethylaminoethyl methacrylate (DMAEMA) monomer. On the other hand, the AD-modified polymeric guest was obtained by ATRP of methyl methacrylate (MMA) using an AD-modified initiator. Because of the molecular recognition between beta-CDs and adamantyl moieties, the polymeric host and guest formed a star-shaped ABC miktoarm terpolymer via a simple mixing procedure. The resultant ABC miktoarm star-shaped terpolymer was characterized by two-dimensional NMR spectroscopy. This amphiphilic ABC miktoarm terpolymer could self-assemble into micelles in aqueous solution, and the reversible transition between assembly and disassembly of this supramolecular ABC miktoarm star terpolymer could be readily controlled by adding the competitive host or guest.