Chain stiffness of cellulose tris(phenylcarbamate) in tricresyl phosphate (TCP)

Abstract

Small-angle X-ray scattering (SAXS) measurements were carried out for two cellulose tris(phenylcarbamate) (CTPC) samples in tricresyl phosphate (TCP) at 25 C to determine the particle scattering function P(q) and the z-average mean-square radius of gyration S 2  z. The obtained data were analyzed in terms of the wormlike chain model to estimate the Kuhn segment length  −1 (the stiffness parameter, equivalent to twice the persistence length) and the helix pitch (or helix rise) per residue h. The resultant  −1 and h were 11.5  0.5 nm and 0.51 nm, respectively. While the latter value (h) is consistent with the previously reported values both for cellulose and cellulose derivatives, appreciably higher chain flexibility was found for CTPC in TCP than that in tetrahydrofuran at 25 C (19-24 nm). The value is fairly close to that in anisol, cyclohexanol, and benzophenone assuming an appropriate temperature coefficient. We may thus conclude that CTPC behaves as a semiflexible chain in TCP.

Viscoelastic Properties of Tightly Entangled Semiflexible Polymer Solutions

“…Recently, Jiang et al. reported that cellulose tris­(phenyl carbamate) (CTC), which is known as a semiflexible polymer, with λ –1 = 11.5 nm, can be dissolved into tricresyl phosphate (TCP), and they measured its chain dimensions in TCP via small angle X-ray scattering. , TCP is a glass-forming solvent, and we can change its viscosity by changing the temperature. Thus, solutions of CTC in TCP are anticipated to be an ideal system for viscoelastic measurements over a wide temperature/frequency range.…”

Molecular Conformation and Intermolecular Interactions of Linear and Cyclic Amylose Derivatives in Solution

“…[ 31 ] On the other hand, the chain stiffness L K distributes in a wider range from 9 to 75 nm. The highest value is smaller than double helical xanthan [ 32 ] and triple helical schizophyllan [ 33 ] but still much larger than that for amylose, [ 34,35 ] cellulose carbamates, [ 36–38 ] and hyaluronan. [ 39,40 ] The chain stiffness for amylose carbamates with small side groups, ATEC and ATBC, is mostly determined by the intramolecular hydrogen bonding between NH and C=O groups on the neighboring glucose units.…”