The static structure of polyrotaxane in solution investigated by contrast variation small-angle neutron scattering

Polyrotaxane (PR) possesses a supramolecular structure in which cyclic molecules are threaded into an axial polymer. In this study, the static structure of PR dissolved in a good solvent was investigated using contrast variation small-angle neutron scattering. The conformation of the axial linear polymer and the alignment of cyclic molecules within the axial polymer were evaluated quantitatively with the help of a detailed derivation of scattering theory. The decomposed partial scattering functions of the cyclic molecules and the axial polymer and the cross-correlation between cyclic molecules and an axial polymer strongly supported the idea that the alignment of cyclic molecules threaded on the axial polymer is random. On the basis of experimental observation, the entropic origin of the stiffening of PR due to the array of cyclic molecules is discussed. Polymer Journal (2011) 43, 155-163; doi: 10.1038/pj.2010.124; published online 8 December 2010