1 research outputs found
Solution Properties of a Cyclic Chain Having Tunable Chain Stiffness: Cyclic Amylose Tris(<i>n</i>‑butylcarbamate) in Θ and Good Solvents
Small-angle X-ray scattering measurements
were made for nine cyclic amylose trisÂ(<i>n</i>-butylcarbamate)
(cATBC) samples ranging in the weight-average molar mass <i>M</i><sub>w</sub> from 1.6 × 10<sup>4</sup> to 1.1 × 10<sup>5</sup> to determine the <i>z</i>-average mean-square radius
of gyration ⟨<i>S</i><sup>2</sup>⟩<sub><i>z</i></sub> and the particle scattering function <i>P</i>(<i>q</i>) 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 <i>M</i><sub>w</sub>, the second virial coefficient <i>A</i><sub>2</sub>, and the hydrodynamic radius <i>R</i><sub>H</sub>. 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<sup>–1</sup> 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 <i>A</i><sub>2</sub> values, (1.3–1.4) × 10<sup>–4</sup> mol
g<sup>–2</sup> cm<sup>3</sup>. It is successfully explained
by the simulation results considering intermolecular topological interaction