Abstract
The rotating frame 13C spin-lattice relaxation time for poly(γ-benzyl L-glutamate) (PBLG) in the solid state was measured by the cross polarization/magic angle spinning (CP/MAS) NMR. From the 13C spin-lock frequency dependence of ‘observed’ relaxation time T1ρ*, it was revealed that the spin-lattice process with a relaxation time T1ρ is dominant rather than the spin-spin process. Thus, T1ρ measurement gives the information about the dynamical behaviors in PBLG. The temperature dependence of T1ρ was investigated above room temperature. The T1ρ∼temperature curves for side chain carbons showed a minimum, whose value is much larger than the expected one for the isotropic motion with a single distribution of the correlation time. It was suggested that side chain motion is highly anisotropic and/or the distribution of the correlation time is excessively broad. However, the temperature causing such a T1ρ minimum is very close to that for previously reported β-process corresponding to motion of whole side chain. Further, T1ρ results showed that the motion of benzyl group at the end of side chain contributes dominantly to the β-process. The effect of MAS rate on T1ρ is briefly discussed.
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References
M. Tsuboi, J. Polym. Sci., 59, 139 (1962).
J. Watanabe and I. Uematsu, Polymer, 25, 1711 (1984).
A. Tsutsumi, K. Hikichi, and M. Kaneko, Polym. J., 10, 437 (1978).
A. Tsutsumi, K. Hikichi, T. Takahashi, Y. Yamashita, M. Matsushima, M. Kanke, and M. Kaneko, J. Macromol. Sci., Phys., B8, 413 (1973).
J. Ferry, “Viscoelastic Properties of Polymers,” John Wiley and Sons Inc., New York, N.Y., 1962.
D. L. VanderHart and A. N. Garroway, J. Chem. Phys., 71, 2773 (1979).
J. Schaefer, E. O. Stejskal, T. R. Steger, M. D. Sefcik, and R. A. Mckay, Macromolecules, 13, 1121 (1980).
J. Schaefer, E. O. Stejskal, and R. Buchdahl, Macromolecules, 10, 384 (1977).
A. Shoji, T. Ozaki, H. Saito, R. Tabeta, and I. Ando, Macromolecules, 17, 1472 (1984).
A. N. Garroway, J. Magn. Reson., 34, 263 (1979).
A. Tsutsumi, S. Anzai, and K. Hikichi, Polym. J., 15, 355 (1983).
M. Mehring, “Principles of High Resolution NMR in Solids,” Springer-Verlag, Berlin, 1983.
D. E. Demco, J. Tegenfeld, and J. S. Waugh, Phys. Rev., 11, 4113 (1975).
K. Akasaka, S. Ganapathy, C. A. McDowell, and A. Naito, J. Chem. Phys., 78, 3567 (1983).
T. T. P. Ceung and R. Yaris, J. Chem. Phys., 72, 3604 (1980).
U. Haeberlen and J. S. Waugh, Phys. Rev., 185, 420 (1969).
P. J. Flory, “Statistical Mechanics of Chain Molecules,” Interscience, New York, N.Y., 1969.
V. J. McBriety, Polymer, 15, 503 (1974).
G. Lipari and A. Szabo, J. Chem. Phys., 104, 4559 (1982).
Y. Yamashita, A. Tsutsumi, K. Hikichi, and M. Kaneko, Polym. J., 8, 14 (1975).
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Yamaguchi, M., Tsutsumi, A. Side Chain Dynamics in Poly(γ-benzyl L-glutamate) as Studied by High-Resolution Solid State 13C Nuclear Magnetic Relaxation in Rotating Frame. Polym J 25, 131–139 (1993). https://doi.org/10.1295/polymj.25.131
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DOI: https://doi.org/10.1295/polymj.25.131