En route to intelligent hydrogels: Copolymers of N‐isopropylacrylamide containing adamantyl groups can be cross‐linked noncovalently with cyclodextrin dimers. This results in thermosensitive hydrogels with cloud points that are lower than those of the pure copolymers. Addition of monomeric methylated cyclodextrin results in an increase in the cloud points but has no significant influence on the viscosity of the copolymer solution.

alpha-Cyclodextrin with a p-t-butoxyaminocinnamoylamino group in the 3-position (3-p-(t)()BocCiNH-alpha-CD) has been found to form a supramolecular polymer in an aqueous solution. The degree of polymerization of the supramolecular polymer is higher than 15 at 20 mM, as proved by VPO (vapor pressure osmometry) measurements and turbo ion spray TOF MS measurements. The existence of substitution/substitution interactions between adjacent monomers of the supramolecular polymer have been confirmed by the observation of positive and negative Cotton bands in circular dichroism spectra. The mechanism for the induction of the chirality was confirmed using model compounds. The substituents were found to exist as a left-handed anti configuration in supramolecular polymers. The supramolecular polymer was found to take a helical structure. The structure of the supramolecular polymer was observed by STM measurements.

Supramolecular polymers having alternating alpha- and beta-cyclodextrin (CD) units have been prepared by using conformational change induced by competitive guests. Although each CD unit does not form intermolecular complexes, a mixture of an alpha-CD derivative and a beta-CD derivative formed intermolecular complexes to give supramolecular polymers having alternating CD units. This is the first example of construction of supramolecular polymers with alternating alpha-, beta-cyclodextrin units.

The copolymers of acrylamide and acrylamide with pendant azobenzene (AzBA–AAm) were prepared by radical polymerization. The association constants of trans-AzBA–AAm copolymers with β-CD are larger than those of cis-AzBA–AAm copolymers. The trans-AzBA–AAm guest copolymer was found to form supramolecular gels with β-CD–pAA (pAA; poly(allylamine)) host copolymers in water.

Novel supramolecular polymers have been prepared from a β-cyclodextrin dimer and a ditopic guest dimer having adamantyl groups. β-Cyclodextrins were bound to poly(ethylene glycol) (PEG, M n 600). Adamantyl groups were also bound to PEG (M n 600). The ROESY NMR spectrum of a 1:1 mixture of the β-cyclodextrin dimer and the ditopic adamantane guest dimer showed ROE correlations between the protons of adamantyl substituents and the inner protons of β-cyclodextrin. Molecular weights and molecular sizes of the supramolecular polymer constructed by the mixture of the β-cyclodextrin dimer and the ditopic adamantane guest dimer were investigated by the pulse field gradient spin echo (PFGSE) NMR and by vapor pressure osmometry (VPO). The results have shown that the mixture of the β-cyclodextrin host dimer and the adamantane guest dimer gave linear supramolecular polymers with high molecular weight (M n = 100 000).