Cyclodextrins thread onto polymer chains to form inclusion complexes, espec
ially when the polymer is hydrophobic relative to the solvent. Selective th
reading might occur when the polymer architecture contains both hydrophobic
and hydrophilic segments. alpha -Cyclodextrin formed crystalline inclusion
complexes with (AB)(n) microblock copolymers, where the A block was a line
ar alkyl segment containing a single double bond and the B block was an exa
ct length segment of poly(ethylene oxide). The complexes were isolated and
characterized by solution and solid-state NMR, X-ray diffraction, different
ial scanning calorimetry, and thermogravimetric analysis. Each method confi
rmed complex formation and showed that the physical properties of the compl
exes were distinct from those of its individual components. The X-ray data
were consistent with known inclusion complexes having a channel or column c
rystal structure. The stoichiometry of the complex formation, 2.3 alpha -cy
clodextrin rings per polymer repeat unit, was determined by NMR analysis of
the complexes and from an analysis of the inclusion complex yields. The da
ta suggest that the inclusion complex stoichiometry is defined by the incre
asing insolubility of the polymer-cyclodextrin complex. Solid-state NMR dat
a were consistent with a preference for threading onto hydrophobic segments
of the (AB)(n) polymer. (C) 2001 John Wiley & Sons, Inc.