Temperature sensitive supramolecular self assembly of per-6-PEO-ß-cyclodextrin and α,ω-di-(adamantylethyl)poly(N-isopropylacrylamide) in water.

The host/guest interactions in water of a star polymer consisting of a ß-cyclodextrin (ß-CD) core bearing six poly(ethylene oxide) arms linked to the C6 positions of ß-CD (ß-CD-PEO7, Mn 5000 g mol(-1)) and α,ω-di-(adamantylethyl)poly(N-isopropylacrylamide) (Ad-PNIPAM-12K, Mn 12,000 g mol(-1)) were studied by 1D and 2D (1)H and (13)C NMR spectroscopy, isothermal calorimetry (ITC), and light scattering (LS). In cold water (T < 26 °C) supramolecular "dumbbell" assemblies, consisting of PNIPAM chains with ß-CD/Ad inclusion complexes at each end, formed viaß-CD-insertion of the terminal Ads through the ß-CD secondary face. Light scattering, microcalorimetry (DSC), and DOSY NMR studies indicated that mixed aqueous solutions of ß-CD-PEO7 and Ad-PNIPAM-12K undergo a reversible heat-induced phase transition at ∼32 °C, accompanied by a release of a fraction of the Ad-bound ß-CD-PEO7 into bulk solution and the formation of aggregated Ad-PNIPAM-12K stabilized by a ß-CD-PEO7 shell.

High conversion synthesis of pyrene end functionalized polyrotaxane based on poly(ethylene oxide) and alpha-cyclodextrins.

We describe the quantitative synthesis of new pyrene labeled cyclodextrin-based polyrotaxane starting from pseudopolyrotaxane of alpha,omega-dimethacrylate poly(ethylene oxide) (PEO) and alpha-cyclodextrins (alpha-CDs). Using a solvent mixture (H2O/dimethyl sulfoxide (DMSO)), an almost quantitative conversion in polyrotaxane can be achieved using the coupling reaction between methacrylic functions and 1-pyrene butyric acid N-hydroxysuccinimide ester. This result is due to the fast blocking reaction of the pseudopolyrotaxane telechelic functions. The polyrotaxanes are characterized by NMR, size exclusion chromatography (SEC), and small-angle neutron scattering (SANS). A rodlike structure of the polyrotaxane is evidenced by SANS, and a persistence length of 70 A is determined. This result corresponds to an almost completely stretched PEO chain of 1000 g.mol(-1) molecular weight. We furthermore studied the opposite case of low packing density polyrotaxanes that were also silylated to suppress interactions between cyclodextrins. We observed a random coil structure only for silylated low packed polyrotaxane. This result demonstrates that both hydrogen bonding and packing density can explain the rodlike structure of cyclodextrin-based polyrotaxane.