Detalle Publicación

Threading different rings on x-shaped block copolymers: hybrid pseudopolyrotaxanes of cyclodextrins and tetronics

Autores: Puig Rigall, Joan; Serra Gómez, Rafael; Guembe-Michel, N.; Grillo, I. ; Dreiss, C. A. ; González Gaitano, Gustavo (Autor de correspondencia)
Título de la revista: MACROMOLECULES
ISSN: 0024-9297
Volumen: 53
Número: 8
Páginas: 3166 - 3174
Fecha de publicación: 2020
Pseudopolyrotaxanes (PPRs) are supramolecular host-guest complexes constituted by the reversible threading of macrocycles along a polymer chain. We report the formation of hybrid PPRs (hPPRs), where two types of cyclodextrins (CDs) thread either simultaneously or sequentially on four-arm poly-(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block copolymers (Tetronic): native alpha-CD (CD) (with higher affinity for PEO) and dimethylated beta-CD (DIMEB, with higher affinity for PPO). The competitive complexation along the chains is examined with three Tetronics, differing mainly in the length of their PEO blocks: T904, T1107, and T1307. While PPRs formed with alpha-CD are insoluble, due to the hydrogen-bond network formed between adjacent alpha-CDs, the presence of DIMEB leads to soluble hybrid PPRs, slows down the kinetics of complexation, and increases the number of alpha-CDs threaded per arm. The morphology of the constructs in solution over time is followed by time-resolved small-angle neutron scattering (TR-SANS), while their crystalline structure is studied by X-ray diffraction. Whereas the complexation of the polymeric surfactant with DIMEB shifts the unimer-micelle equilibrium toward unimers, the presence of alpha-CD slows down demicellization and reduces its extent. Overall, the co-threading of two cyclodextrins on the same polymer provides a handle to tune the complexation process and the final properties of the PPR, including solubility, kinetics of complexation, and composition of the complexes.