Rigid Cyclic Polymer in Solution: Cycloamylose Tris(phenylcarbamate) in 1,4-Dioxane and 2-Ethoxyethanol

Six cyclic amylose tris(phenylcarbamate) (ATPC) samples have been prepared from enzymatically synthesized cyclic amylose ranging in the number of repeat units N from 24 to 290. Synchrotron-radiation small-angle X-ray scattering measurements were made for the samples in 1,4-dioxane (DIOX) and 2-ethoxyethanol (2EE) to determine the z-average radius of gyration ⟨S²⟩ and the particle scattering function P(q). Molar mass dependencies of ⟨S²⟩ in the two solvents were successfully explained by the current theories for the wormlike ring with the same parameters for linear ATPC in the corresponding solvent, that is, the helix pitch h (or contour length) per residue and the Kuhn segment length λ^-1 (stiffness parameter, twice the persistence length). The latter parameter λ^-1 is 22 and 16 nm in DIOX and 2EE, respectively. Except for the low-q region, P(q) was also explained by the rigid ring having the same contour length Nh as that for linear ATPC. Further, their local conformation estimated from circular dichroism spectra is essentially unaltered from that for linear ATPC at least when N ≥ 24.