Abstract
The temperature and molecular weight dependencies of the intrinsic viscosity [η] were investigated for cellulose tris(phenyl carbamate) (CTC) in tetrahydrofuran (THF). By the analysis of the [η] data in terms of the wormlike cylinder model, the persistence length q of CTC was determined as a function of the temperature. With decreasing the temperature from 25 to −20 °C, q increases from 10.5 to 13.7 nm. This temperature dependence of q was successfully explained by the broken wormlike chain model, where each glucose residue in the cellulosic chain is assumed to take left-handed 3/1 or 2/1 helical state and occasionally a kink state generated by a glucosidic bridge angle fluctuation. While the torsional fluctuation in each glucosidic bond is considerably small, there are two energetically favored helical (3/1 and 2/1) states, so that the cellulosic chain may not be regarded as a regular helix in solution.
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M. M. Green, N. C. Peterson, T. Sato, A. Teramoto, R. Cook, and S. Lifson, Science, 268, 1860 (1995).
M. M. Green, J.-W. Park, T. Sato, A. Teramoto, S. Lifson, R. L. B. Selinger, and J. V. Selinger, Angew. Chem., Int. Ed., 38, 3138 (1999).
T. Nakano and Y. Okamoto, Chem. Rev., 101, 4013 (2001).
M. Fujiki, J. R. Koe, K. Terao, T. Sato, A. Teramoto, and J. Watanabe, Polym. J., 35, 297 (2003).
T. Sato, K. Terao, A. Teramoto, and M. Fujiki, Polymer, 44, 5477 (2003).
R. S. Werbowyj and D. G. Gray, Mol. Cryst. Liq. Cryst. (Lett.), 34, 97 (1976).
R. S. Werbowyj and D. G. Gray, Macromolecules, 13, 69 (1980).
Y. Okamoto and E. Yashima, Angew. Chem., Int. Ed., 37, 1020 (1998).
F. Kasabo, T. Kanematsu, T. Nakagawa, T. Sato, and A. Teramoto, Macromolecules, 33, 2748 (2000).
J. Danhelka, M. Netopilik, and M. Bohdanecky, J. Polym. Sci., Part B: Polym. Phys., 25, 1801 (1987).
T. Sato, T. Shimizu, F. Kasabo, and A. Teramoto, Macromolecules, 36, 2939 (2003).
T. Sato, M. Hamada, and A. Teramoto, Macromolecules, 36, 6840 (2003).
T. Kanematsu, T. Sato, Y. Imai, K. Ute, and T. Kitayama, Polym. J., 37, 65 (2005).
D. A. Brant and K. D. Goebel, Macromolecules, 8, 522 (1975).
K. D. Goebel, C. E. Harvie, and D. A. Brant, Appl. Polym. Symp., 28, 671 (1976).
D. A. Brant, Q. Rev. Biophys., 9, 527 (1976).
B. A. Burton and D. A. Brant, Biopolymers, 22, 1769 (1983).
B. Hsu, C. A. McWherter, D. A. Brant, and W. Burchard, Macromolecules, 15, 1350 (1982).
T. Sato, K. Terao, A. Teramoto, and M. Fujiki, Macromolecules, 35, 2141 (2002).
S. Lifson, C. Andreola, N. C. Peterson, and M. M. Green, J. Am. Chem. Soc., 111, 8850 (1989).
M. L. Mansfield, Macromolecules, 19, 854 (1986).
A. K. Gupta, E. Marchal, and W. Burchard, Macromolecules, 8, 843 (1975).
D. W. Tanner and G. C. Berry, J. Polym. Sci., Polym. Phys. Ed., 12, 941 (1974).
J. W. Noordermeer, R. Daryanani, and H. Janeschitz-Kriegl, Polymer, 16, 359 (1975).
W. Burchard, Br. Polym. J., 3, 214 (1971).
S. Dayan, P. Maissa, M. J. Vellutini, and P. Sixou, Polymer, 23, 800 (1982).
H. Yamakawa and M. Fujii, Macromolecules, 7, 128 (1974).
H. Yamakawa and T. Yoshizaki, Macromolecules, 13, 633 (1980).
H. Yamakawa, “Helical Wormlike Chains in Polymer Solutions,” Springer-Verlag, Berlin & Heidelberg, 1997.
H. Yamakawa and W. H. Stockmayer, J. Chem. Phys., 57, 2843 (1972).
H. Yamakawa and J. Shimada, J. Chem. Phys., 83, 2607 (1985).
J. Shimada and H. Yamakawa, J. Chem. Phys., 85, 591 (1986).
T. Yoshizaki and H. Yamakawa, J. Chem. Phys., 81, 982 (1984).
S. S. C. Chu and G. A. Jeffrey, Acta Crystallogr., Sect. B: Struct. Sci., 24, 830 (1968).
C. V. Goebel, W. L. Dimpfl, and D. A. Brant, Macromolecules, 3, 644 (1970).
Y. Nakata, S. Kitamura, K. Takeo, and T. Norisuye, Polym. J., 26, 1085 (1994).
The torsional angles φ and ψ in Figure 5a are defined as the dihedral angles formed by the atoms H(1)C(1)O(1)C(4′) and C(1)O(1)C(4′)H(4′), respectively, measured relative to the cis conformation and being positive at the clockwise rotation along the vectors C(1)O(1) and O(1)C(4′), respectively. In the three-bond model (in Figure 5b), the bond angles θ1, θ2, and θ3 (=β) are defined as the angles formed by bonds 1 and 2, bonds 2 and 3, and bonds 3 and 1, respectively, while the torsional angles \\tildeφ1 and \\tildeφ3 are defined as the dihedral angles formed by the three bonds b3b1b2 and b2b3b1, respectively, measured relative to the trans conformation and being positive at the clockwise rotation along the vectors b1 and b3, respectively. From the crystallographic data for cellobiose, 33 we have the relations: \\tildeφ1=ψ+9.2° and \\tildeφ3=φ+6.6°.
D. A. Brant and W. L. Dimpfl, Macromolecules, 3, 655 (1970).
S. S. C. Chu and G. A. Jeffrey, Acta Crystallogr., 23, 1038 (1967).
As demonstrated by Burton and Brant, 17 the configurational entropy ΔSc of the cellulosic chain is considerably larger than that of amylosic chain, but it should be noted that the 3/1 and 2/1 helical states in the cellulosic chain are not distinguished in ΔSc in contrast with the standard deviations 〈(\\tildeφi−\\tildeφi,3/1)2〉1/2 and 〈(\\tildeφi−\\tildeφi,2/1)2〉1/2 (i=2,3) in our argument.
R. C. Jordan, D. A. Brant, and A. Cesaro, Biopolymers, 17, 2617 (1978).
M. Fujii, K. Nagasaka, J. Shimada, and H. Yamakawa, Macromolecules, 16, 1613 (1983).
H. Bitteiger and G. Keilich, Biopolymers, 7, 539 (1969).
Y. Ashida, T. Sato, K. Morino, K. Maeda, Y. Okamoto, and E. Yashima, Macromolecules, 36, 3345 (2003).
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Yanai, H., Sato, T. Local Conformation of the Cellulosic Chain in Solution. Polym J 38, 226–233 (2006). https://doi.org/10.1295/polymj.38.226
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DOI: https://doi.org/10.1295/polymj.38.226