Eight amylose tris(ethylcarbamate) (ATEC) samples ranging in the weight-average molar mass M(w) from 1.0 × 10(4) to 1.1 × 10(6) g mol(-1) and five amylose tris(n-hexylcarbamate) (ATHC) samples of which M(w) varies from 4.9 × 10(4) to 2.2 × 10(6) g mol(-1) have been prepared from enzymatically synthesized amylose samples having narrow dispersity indices and no branching. Small-angle angle X-ray scattering (SAXS), light scattering, viscometry, and infrared (IR) absorption measurements were carried out for their dilute solutions, that is, ATEC in tetrahydrofuran (THF), 2-methoxyethanol (2ME), methanol (MeOH), and ATHC in THF and 1-propanol (1PrOH) to determine M(w), particle scattering functions, intrinsic viscosities, and IR spectra. SAXS and viscosity measurements were also made on ATEC in d- and l-ethyl lactates. The data were analyzed in terms of the wormlike cylinder model to estimate the helix pitch (or contour length) per residue h and the Kuhn segment length λ(-1) (stiffness parameter, twice the persistence length). Both ATEC and ATHC have large λ(-1) in THF, that is, 33 and 75 nm, respectively, and smaller λ(-1) were obtained in alcohols, indicating that they have rigid helical conformation stabilized by intramolecular hydrogen bonds in THF. On the contrary, the helical structure estimated from the h value significantly depends on the alkyl side groups in a complex fashion, that is, h = 0.36 nm for ATEC, h = 0.29 nm for ATHC, and h = 0.26 nm for amylose tris(n-butylcarbamate) (ATBC). This is likely related to the bulkiness of side groups packed inside the amylosic helices. The solvent dependence of h, λ(-1), and the fraction f(hyd) of intramolecular hydrogen bonds for ATEC can be explained by a current model as is the case with ATBC [ Terao , K. ; Macromolecules 2010 , 43 , 1061 ], in which each contour point along the chain takes loose helical and rigid helical sequences independently.

Lyotropic liquid crystallinity was investigated for amylose tris(n-butylcarbamate) (ATBC), amylose tris(ethylcarabamate) (ATEC), and amylose tris(n-hexylcarbamate) (ATHC) in tetrahydrofuran (THF) and ethyl lactates (ELs) by using phase separation experiments, polarized microscopic observation, small-angle X-ray diffraction, and circular dichroism measurements. Concentrated THF solution of ATBC has selective reflection at visible light wavelength, indicating the formation of cholesteric phase. A current theory well explains the phase diagram of ATBC, ATEC, and ATHC in THF. On the other hand, ELs solution forms smectic phase and it has significantly different phase diagram, that is, the biphasic range is much wider than that in THF. In other words, highly concentrated smectic phase can be obtained from semidilute and rather low viscosity ELs solution. This is likely because amylose alkylcarbamate chains may have significant anisotropic intermolecular attractive interaction in between polymer chains in ELs or intermolecular interactions between the chain ends are much more different from those in THF.

Small-angle X-ray scattering measurements were made for nine cyclic amylose tris(n-butylcarbamate) (cATBC) samples ranging in the weight-average molar mass M w from 1.6 × 104 to 1.1 × 105 to determine the z-average mean-square radius of gyration ⟨S 2⟩ z and the particle scattering function P(q) in two good solvents, tetrahydrofuran (THF) and methanol (MeOH) at 25 °C and in a Θ solvent, 2-propanol (2PrOH) at the Θ temperature (35 °C). Static and dynamic light scattering measurements were carried out for cATBC in 2PrOH to determine M w, the second virial coefficient A 2, and the hydrodynamic radius R H. The dimensional and hydrodynamic properties are consistently explained by the current theories for wormlike ring having substantially the same model parameters obtained for linear analogues, that is, the Kuhn segment length λ–1 of THF, 2PrOH, and MeOH are 75, 20, and 11 nm, respectively. Furthermore, number of hydrogen bonds decreases with the order of THF, 2PrOH, and MeOH, as is the case with linear ATBC. These results indicate that cATBC has rigid helical backbone stabilized by intramolecular hydrogen bonds in THF and it loosens with increasing solvent polarity. Indeed, lyotropic liquid crystallinity was found for cATBC in THF. In the Θ condition, 2PrOH at 35 °C, cATBC has large positive A 2 values, (1.3–1.4) × 10–4 mol g–2 cm3. It is successfully explained by the simulation results considering intermolecular topological interaction.

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