title: Hydrogels composed of organic amphiphiles and alpha-cyclodextrin: supramolecular networks of their pseudorotaxanes in aqueous media.
abstract: Mixtures of N-alkyl pyridinium compounds [py-N-(CH(2))(n)OC(6)H(3)-3,5-(OMe)(2)](+)(X(-)) (1bCl: n = 10, X = Cl; 1cBr: n = 12, X = Br) and alpha-cyclodextrin (alpha-CD) form supramolecular hydrogels in aqueous media. The concentrations of the two components influences the sol-gel transition temperature, which ranges from 7 to 67 degrees C. Washing the hydrogel with acetone or evaporation of water left the xerogel, and (13)C CP/MAS NMR measurements, powder X-ray diffraction (XRD), and scanning electron microscopy (SEM) revealed that the xerogel of 1bCl (or 1cBr) and alpha-CD was composed of pseudorotaxanes with high crystallinity. (13)C{(1)H} and (1)H NMR spectra of the gel revealed the detailed composition of the components. The gel from 1bCl and alpha-CD contains the corresponding [2]- and [3]pseudorotaxanes, [1b x (alpha-CD)]Br and [1b x (alpha-CD)(2)]Br, while that from 1cBr and alpha-CD consists mainly of [3]pseudorotaxane [1c x (alpha-CD)(2)]Br. 2D ROESY (1)H NMR measurements suggested intermolecular contact of 3,5-dimethoxyphenyl and pyridyl end groups of the axle component. The presence of the [3]pseudorotaxane is indispensable for gel formation. Thus, intermolecular interaction between the end groups of the axle component and that between alpha-CDs of the [3]pseudorotaxane contribute to formation of the network. The supramolecular gels were transformed into sols by adding denaturing agents such as urea, C(6)H(3)-1,3,5-(OH)(3), and [py-N-nBu](+)(Cl(-)).
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagastuta, Midori-ku, Yokohama 226-8503, Japan.
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Taira
authors.forename: Yuji
authors.initials: Y
authors.lastname: Suzaki
authors.forename: Kohtaro
authors.initials: K
authors.lastname: Osakada