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A novel triblock macromolecular architecture based on cyclodextrin (CD) complexation is presented. A CDfunctionalized biocompatible poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) building block (3800 ≤ M n ≤ 10 600 g mol −1 ; 1.29 ≤ Đ M ≤ 1.46) and doubly guestcontaining poly(N,N-dimethylacrylamide) (PDMAAm) (6400 ≤ M n ≤ 15 700 g mol −1 ; 1.06 ≤ Đ M ≤ 1.15) and poly(N,Ndiethylacrylamide) (PDEAAm) (5400 ≤ M n ≤ 12 100 g mol −1 ; 1.11 ≤ Đ M ≤ 1.33) segments were prepared via reversible addition−fragmentation chain transfer (RAFT) polymerization and subsequently utilized for the formation of a well-defined supramolecular ABA triblock copolymer. The block formation was evidenced via dynamic light scattering (DLS), nuclear Overhauser effect spectroscopy (NOESY), and turbidity measurements. Furthermore, the connection of the blocks was proven to be temperature responsive andin the case of azobenzene guestsresponsive to the irradiation with UV light. The application of these stimuli leads to the disassembly of the triblock copolymer, which was shown to be reversible. In the case of PDEAAm containing triblock copolymers, the temperatureinduced aggregation was investigated as well.

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The synthesis of a new glycomonomer based on mannose, prepared via CuAAC, is reported. The resulting 1,2,3-triazole linkage between mannose and the polymer backbone ensures the formation of highly stable glycopolymers, which will not undergo hydrolysis. The monomer 2'-(4-vinyl-[1,2,3]-triazol-1-yl)ethyl-O-alpha-D-mannopyranoside was polymerized in the presence of a RAFT agent - 3-benzylsulfanylthiocarbonylsulfanyl propionic acid - to yield well-defined polymers with molecular weights up to 51,500 g mol(-1) and a PDI of 1.16. The resulting polymer was employed as a macroRAFT agent in the polymerization of NIPAAm in order to generate thermo-responsive block copolymers, which undergo reversible micelle formation at elevated temperatures. The rapid interaction between the polymers prepared and ConA confirms the high affinity of these structures to proteins. While the linear glycopolymers already undergo a fast complexation with ConA, the reported rates have found to be exceeded by the micellar glycopolymer structure presented in the current contribution.