Temperature-responsive inclusion complex of cationic PNIPAAM diblock copolymer and γ-cyclodextrin

Aqueous mixtures of gamma-cyclodextrin (gamma-CD) and the thermosensitive cationic diblock copolymer poly(N-isopropylacrylamide)-b-poly(3-acrylamidopropyl)trimethylammonium chloride (PNIPAAM(24)-b-PAMPTAM(+)(9)) or the PNIPAAM homopolymer PNIPAAM(47) have been investigated using various experimental methods. Solid g-CD-polymer inclusion complexes (pseudopolyrotaxanes) form at ambient temperatures in fairly concentrated CD solutions. The NMR measurements showed that the stoichiometry of the inclusion complexes is close to two NIPAAM units per CD molecule. The cationic block of the copolymer is not incorporated into the CD cavity. Synchrotron radiation X-ray diffraction spectra of the solid inclusion complexes indicate a compact columnar structure of CD molecules threaded onto the PNIPAAM chains. In water, square-shaped cyclodextrin aggregates were found to co-exist with single cyclodextrin molecules. In mixed solutions of gamma-CD and PNIPAAM(24)-b-PAMPTAM(+)(9) these aggregates disintegrate with time as inclusion complexes are formed and the kinetics was studied using time-resolved static and dynamic light scattering and cryo-TEM. Steady-state fluorescence spectroscopy measurements reveal that the CD molecules dethread from the PNIPAAM chains upon increasing the temperature to 40 degrees C, which is above the lower critical solution temperature of PNIPAAM.