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Orientational Order of α-Helical Poly (γ-Benzyl L-Glutamate) in the Lyotrao-Phiecl Ilciaqlu Idp Oclryy(yS-Tbaelnlziynle Ls-Tate and Conformation of the Pendant Side Chain

Published online by Cambridge University Press:  26 February 2011

Akihiro Abe  and
Toshimasa Yamazaki
Akihiro Abe
Affiliation:
Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152, Japan
Toshimasa Yamazaki
Affiliation:
Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152, Japan
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Abstract

Deuterium NMR studies have been performed on variously labeled PBLG samples in the lyotroplc liquid crystalline state. The orientational orders S of the a-helical backbone were estimated from the observed quadrupolar splittings ∆v of the N-D and Cα-D bond. The values of S decrease gradually by dilution until the upper equilibrium concentration (B-point) is reached. The concentration dependence of Scrit has been compared with those derived from standard theories. The relatlve orientation of side chains with respect to the backbone was elucidated by the rotational isomeric state analysis of the ∆v/S data observed for the γ-, γ-, and ζ-methylene, and p-benzyl deuterons. The results indicate that the steric overlaps between adjacent side chains play an important role in determining the preference of conformations in the PBLG system. A similar analysis has been extended to poly(L-glutamic acid) esters carrying a homologous series of ester residues, -C(O)O(CH2)nC6D5 with n = 2 and 3. A distinct odd-even oscillation was observed for the orientation of the terminal phenyl groups with n.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 134: Symposium J – Materials Science and Engineering of Rigid-Rod Polymers , 1988 , 53
Copyright
Copyright © Materials Research Society 1989

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References

REFERENCES

1. Onsager, L., Ann. N.Y. Acad. Sci. 51, 627 (1949).Google Scholar
2. Flory, P. J., Proc. R. Soc. London, Ser. A. 234, 73 (1956).Google Scholar
3. Flory, P. J. and Ronca, G., Mol. Cryst. Liq. Cryst. 54, 289, 311 (1979); P. J. Flory, Adv. Polym. Sci. 59, 1 (1984).Google Scholar
4. Lee, S.-D. and Meyer, R. B., J. Chem. Phys. 84, 3443 (1986).CrossRefGoogle Scholar
5. Khokhlov, A. R. and Semenov, A. N., Physica 108A, 546 (1981); 112A, 605 (1982).Google Scholar
6. Odijk, T., Macromolecules 19, 2313 (1986).Google Scholar
7. Chapman, G. E., Campbell, T. D., and McLaughlin, K. A., Nature 225, 639 (1970).CrossRefGoogle Scholar
8. Yamazaki, T. and Abe, A., Polym. J. 19, 777 (1987).CrossRefGoogle Scholar
9. Poliks, M. D., Park, Y. W., and Samulski, E. T., Mol. Cryst. Liq. Cryst. 153, 321 (1987).Google Scholar
10. Samulski, E. T., J. Phys., Paris 40, C3–471 (1979); K. Czarniecka and E. T. Samulski, Mol. Cryst. Liq. Cryst. 63, 205 (1981).Google Scholar
11. Sohma, J. and Tabata, M., Mol. Cryst. Liq. Cryst. 68, 89 (1981).Google Scholar
12. (a)Wee, E. L. and Miller, W. G., J. Phys. Chem. 75, 1446 (1971); W. G. Miller, C. C. Wu, E. L. Wee, G. L. Santee, J. H. Rai, and K. G. Goebel, Pure Appl. Chem. 38, 37 (1974); (b)K. Kubo and K. Ogino, Mol. Cryst. Liq. Cryst. 53, 207 (1979); K. Kubo, ibid., 74, 71 (1981); (c)T. Itou, S. Funada, F. Shibuya, and A. Teramoto, Kobunshi Ronbunshu 43, 191 (1986); T. Sato and A. Teramoto, Kobunshi 37, 278 (1988); (d)S. Sasaki, K. Tokuma, and I. Uematsu, Polym. Bull. 10, 539 (1983).Google Scholar
13. Abe, A., Furuya, H., and Yoon, D. Y., Mol. Cryst. Liq. Cryst. 159, 151 (1988).Google Scholar
14. Yan, J. F., Vanderkooi, G., and Scheraga, H. A., J. Chem. Soc. 49, 2713 (1968).Google Scholar
15. Toriumi, H., Yamazaki, T., Abe, A., and Samulski, E. T., Liq. Cryst. 1, 87 (1986); H. Toriumi, Y. Kusumi, I. Uematsu, and Y. Uematsu, Polym. J. 11, 863 (1979); H. Toriumi, S. Minakuchi, I. Uematsu, and Y. Uematsu, J. Polym. Sci., Phys. Ed. 19, 1167 (1981).CrossRefGoogle Scholar
16. Yamazaki, T., Abe, A., Ono, H., and Toriumi, H., in preparation.Google Scholar
17. Nagao, M., Sasaki, S., Hayashi, T., and Uematsu, I., Polym. Bull. 9, 11 (1983); S. Sasaki, M. Nagao, and M. Gotoh, J. Polym. Sci. 26, 637 (1988).Google Scholar