Summary
Stable nitroxide radicals are now widely employed as spin labels and spin probes for studies of the relaxations and dynamics of synthetic polymers. For the spin label experiment the nitroxide radical is covalently bound to the polymer chain and for the spin probe experiment a small nitroxide molecule is dispersed in the polymer matrix. Methods of preparing spin probes and spin labelled polymers are reviewed briefly in this chapter. The electron spin resonance (ESR) spectra of the probed or labelled polymers are sensitive to motions in the time regime 10−3−10−11 s and methods for extracting this information are described. The scope and limitations of the spin label and probe techniques are illustrated by reference to published work on synthetic polymers in bulk and in solution.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Stone, T. J., Buckman, T., Nordio, P. L. and McConnell, H. M., Proc. Natl. Acad. Sci. US, 1965, 54, 1010.
See, for example, (a) McGaffney, B. J., in: Spin Labelling: Theory and Applications, L. J. Berliner, Ed., 1974, Academic Press, New York
ROZANSTEV, E. G., Free Nitroxyl Radicals (trans, by B.J. Hazzard), 1970, Plenum Press, New York.
Bullock, A. T., Cameron, G. G. and Krajewski, V., J. Phys. Chem., 1976, 80, 1792.
Cafe, M. C. and Robb, I. D., Polymer, 1979, 20, 513.
Törmälä, P., Lattila, H. and Lindberg, J. J., Polymer, 1973, 14, 481.
Wasserman, A. M., Alexandrova, T. A. and Buchachenko, A. L., Eur. Polym. J., 1976, 12, 691.
Wasserman, A. M., Alexandrova, T. A., Kirsch, Yu. E. and Buchachenko, A. L., Eur. Polym. J., 1979, 2, 1051.
Griffith, O. H., Keana, J. F. W., Rottschaeffer, S. and Warlick, T. A., J. Amer. Chem. Soc., 1967, 89, 5072.
Kurosaki, T., Lee, K. W. and Okawara, M., Polym. Sci., Polym. Chem. Ed., 1972, 10, 3298
(a) BOYER, R. F. and KEINATH, S. E. (Eds), Molecular Motions in Polymers by ESR, 1980, (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland
SOHMA, J., ibid., p. 304.
Kusumoto, N. and Sakai, T., Polymer, 1979, 20, 1175.
Keana, J. F., Keana, S. B. and Beetham, D., J. Amer. Chem. Soc., 1967, 89, 3055.
Bullock, A. T., Cameron, G. G. and Smith, P. M., Macromolecules, 1976, 9, 650.
Bullock, A. T., Cameron, G. G. and Smith, P. M., Eur. Polym. J., 1975, 11, 617.
Friedrich, C., NoËl, C., Ramasseul, R. and Rassat, A., Polymer, 1980, 21, 232.
Bullock, A. T., Butter worth, J. H. and Cameron, G. G., Eur. Polym. 1971, 7, 445.
Bullock, A. T., Cameron, G. G. and Smith, P. M., Polymer, 1972, 13, 89.
Bullock, A. T., Cameron, G. G. and Smith, P. M., J. Phys. Chem., 1973, 77, 1635.
BULLOCK, A. T., CAMEОON, G. G. and REDDY, N. K., J. Chem. Soc., Faraday, l, 1978, 74, 727.
Drefahl, G., Hörhold, H-H. and Hoffmann, K. D., J. Prakt. Chem., 1968, 37, 137.
Braun, D., Makromol. Chem., 1959, 30, 85.
BULLOCK, A. T., CAMERON, G. G. and ELSOM, J. M., Polymer, 1977, 18, 930.
Bullock, A. T., Cameron, G. G. and Smith, P. M., Polymer, 1973, 14, 525.
Bullock, A. T., Cameron, G. G. and Elsom, J. M., Polymer, 1974, 15, 74.
Bullock, A. T., Cameron, G. G. and Elsom, J. M., Eur. Polym. J., 1977, 13, 751.
Hatada, K., Kitayama, T., Fujikawa, K., Ohta, K. and Yuki, H., Polymer Reprints, 1980, 21(1), 59.
HUDSON, A. and LUCKHURST, G. R., Chem. Rev., 1969, 69, 191.
FREED, J. H., J. Chem. Phys., 1964, 41, 2077.
Goldman, S. A., Bruno, G. V., Polnaszek, C. F. and Freed, J. H., J. Chem. Phys., 1972, 56, 716.
Wasserman, A. M., Kuznetsov, A. N., Kovarskii, A. L. and Buchachenko, A. L., Zhur. Strukt. Khim., 1971, 12, 609.
KOVARSKII, A. L., WASSERMAN, A. M. and BUCHACHENKO, A. L., in: Molecular Motions in Polymers by ESR, R. F. Boyer and S. E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland, p. 177.
SMITH, P.M., Eur. Polym. J., 1979, 15, 147.
POGGI, G. and JOHNSON, C. S., JR., J. Magn. Resonance, 1970, 3, 436.
FREED, J. H., BRUNO, G. V. and POLNASZEK, C.F., J. Phys. Chem., 1971, 75, 3385.
McCalley, R. C., Shimshick, E. J. and McConnell, H.M., Chem. Phys. Letters, 1972, 13, 115.
Goldman, S. A., Bruno, G. V. and Freed, J.H., J. Phys. Chem., 1972, 76, 1858.
Mason, R. and Freed, J.H., J. Phys. Chem., 1974, 78, 1321.
Kuznetsov, A. N. and Ebert, B., Chem. Phys. Letters, 1974, 25, 342.
FREED, J. H., in: Spin Labelling: Theory and Applications, L. J. Berliner, Ed., 1974, Academic Press, New York.
POLNASZEK, C. F., P Thesis, Cornell University, 1975.
Rabold, G. P., J. Polym. Sci., Parr A-l, 7, 1203, 1969.
DALTON, L. R., ROBINSON, B. H., DALTON, L. A. and COFFEY, P., in: Advances in Magnetic Resonance, vol. 8, J. S. Waugh, Ed., 1976, Academic Press, New York, p. 149.
Thomas, D. D., Dalton, L. R. and Hyde, J. S., J. Chem. Phys., 1976, 65, 3006.
Mailer, C. and Miller, D. M., J. Magn. Resonance, 1978, 32, 289.
ROBINSON, B. H. and DALTON, L. R., Phys., 1980, 72, 1312.
See, for example, McCrum, N. G., Read, B. E. and Williams, G., Anelastic and Dielectric Effects in Polymeric Solids, 1967, Wiley, London.
Bullock, A. T., Cameron, G. G. and Smith, P. M., J. Chem. Soc., Faraday II, 1974, 70, 1202, 1974.
Zimm, B. H., J. Chem. Phys., 1956, 24, 269.
Allerhand, A. and Hailstone, R. K., J. Chem. Phys., 1972, 56, 3718.
Labský, J., Pilaž, J. and KÁlal, J., Macromoleeules, 1977, 10, 1153
Pilaž, J., LabskÁ, J., KÄlal, J. and Freed, J. H., J. Phys. Chem. 1979, 83, 1907.
MILLER, W. G., RUDOLPH, W. T., VEKSLI, Z., COON, D. L., WU, C. C. and LIANG, T. M. in: Molecular Motions in Polymers by ESR, R. F. Boyer and S. E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland, p. 145.
Mason, R. P., Polnaszek, C. F. and Freed, J. H., J. Phys. Chem., 1974, 78, 1324.
Bullock, A. T., Cameron, G. G. and Grant, I. C., Unpublished results.
SOHMA, J. and MURAKAMI, K., in: Molecular Motions in Polymers by ESR, R. F. Boyer and S. E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland, p. 135.
Kramers, H. A., Physica, 1940, 7, 284.
HELFAND, E., J. Chem. Phys., 1971, 54, 4651.
AMERICAN PETROLEUM INSTITUTE, Selected values of physical and thermodynamic properties of hydrocarbons and related compounds, Research Project No. 44 , 1953.
Bhanumathi, A., Indian J. Pure Appl. Phys., 1963, 1, 79.
Heston, W. M., Jr., Henelly, E. J. and Smyth, C. P., J. Amer. Chem. Soc., 1950, 72, 2071.
Wilson, E. B., Adv. Chem. Phys., 1959, 2, 367.
Heatley, F. and Wood, B., Polymer, 1978, 19, 1405.
GRONSKI, W. and MURAYAMA, N., Makromol. Chem., 1978, 179, 1509.
Lang, M-C, Laupretre, F., NoËl, C. and Monnerie, L., J. Chem. Soc., Faraday II, 1979, 75, 349.
MAGEE, M. D., J. Chem. Soc., Faraday II, 1974, 70, 929.
Bullock, A. T., Cameron, G. G., Grant, I. C. and Robb, I. D., Unpublished results.
Porter, R. S. and Johnson, J. F., Chem. Rev., 1966, 66, 4.
Onogi, S., Kobayashi, T., Kojuna, Y. and Taniguchi, Y., J. Appl. Polymer Sci., 1963, 7, 847.
BULLOCK, A. T. and CAMERON, G. G., in: Structural Studies of Macromolecules by Spectroscopic Methods, K. J. Ivin, Ed., 1976, Wiley, New York, p. 273.
BUCHACHENKO, A. L., WASSERMAN, A. M., ALEKSANDROVA, T. A. and KOVARSKII, A.L., in: Molecular Motions in Polymers by ESR, R. F. Boyer and S. E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland, p. 33.
TöRMäLä, P., J. Macromol. Sci.-Rev. Macromol. Chem., 1979, C17(2), 297
P. TöRMäLä and G. WEBER, Polymer, 1978, 19, 1026.
Kumler, P. L. and Boyer, R. F., Macromolecules, 1976, 9, 903.
Braun, D., Törmälä, P. and Weber, G., Polymer, 1978, 19, 598.
KUMLER, P. L., KEINATH, S. E. and BOYER, R. F., Polymer Preprints, 1976, 17(2), 28.
UBERREITER, K. and KANIG, G., Z. Naturforsch., 1951, 6A, 551;Colloid Sci., 1952, 7, 569.
Fox, T. G. and FLORY, P. J., J. Polym. Sci., 1954, 14, 315; J. Appl. Phys., 1950, 21, 581.
Wall, L. A., Roestamsjah, and Aldridge, M. H., J. Res. Nat. Bur. Stand US, 1974, 78A, 447.
Cowie, J.M.G., Eur. Polym. J., 1975, 11, 297.
Keinath, S. E., Kumler, P. L. and Boyer, R.F., Polymer Preprints, 1975, 16(2), 120.
ILLERS, K.H., Kolloid Z. Z. Polym., 1963, 190, 16.
Kontos, E. G. and Slichter, W. P., J. Polym. Sci., 1962, 61, 61.
Cowie, J. M. G. and McEwan, I., Macromolecules, 1977, 10, 1124.
CAMERON, G. G., in: Molecular Motions in Polymers by ESR, R. F. Boyer and S. E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland, p. 55; BULLOCK, A. T., CAMERON, G. G. and REDDY, N. K., Unpublished results.
BEUCHE, F., Physical Properties of Polymers, 1962, Wiley, New York.
KUSUMOTO, N., SANO, S., ZAITSU, N. and MOTOZATO, Y., Polymer, 1976, 17, 448
KUSUMOTO, N., in: Molecular Motions in Polymers by ESR, R. F. Boyer and S.E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol.1), Harwood, Chur. Switzerland, p. 223.
Bullock, A. T., Cameron, G. G., Howard, C. B. and Reddy, N.K., Polymer, 1978, 19, 352.
Bullock, A. T., Cameron, G. G. and Miles, I. M., Unpublished results.
Kusumoto, N. and Sakai, T., Polymer, 1979, 20, 1175.
TöRMäLä, P., WEBER, G. and LINDBERG, J.J., in: Molecular Motions in Polymers by ESR, R. F. Boyer and S.E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland, p. 81.
Kovarskii, A. L., Plaek, J. and Szöcs, F., Polymer, 1978, 19, 1137
Kovarskii, A. L., Wasserman, A. M. and Buchachenko, A.L., in: Molecular Motions in Polymers by ESR, R. F. Boyer and S. E. Keinath, Eds., 1980 (MMI Press Symposium Series, Vol. 1), Harwood, Chur, Switzerland, p. 177.
Törmälä, P., J. Appl. Polym. Sci., 1978, 22, 2077.
Bullock, A. T., Cameron, G. G. and Smith, P. M., J. Polym. Sci., Polym. Phys. Ed., 1973, 11, 1263.
Bordeaux, D., Lajzerowicz, J., Brière, R., Lemaire, H. and Rassat, A., Org. Magn. Res., 1973, 5, 47.
Capiomont, A., Chion, B., Lajzerowicz, J. and Lemaire, H., J. Chem. Phys., 1974, 60, 2530.
Griffith, O. H., Cornell, D. W. and Monnell, H. M., J. Chem. Phys., 1965, 43, 2909.
SNIPES, N., CUPP, J., COHN, G. and KEITH, A., Biophys. J., 1974, 14, 20.
BERLINER, L. J. (Ed.), Spin Labelling Theory and Application, 1976, Academic Press, New York, Chapter 2, p. 32.
GORDON, R. G. and MESSENGER, T., in Electron Spin Relaxation in Liquids, L.T. Muus and P. W. Atkins, Eds., 1972, Plenum Press, London and New York, p. 371.
KUZNETSOV, A. N. et al., Chem. Phys. Letters, 1971, 12, 103.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1982 Applied Science Publishers Ltd
About this chapter
Cite this chapter
Cameron, G.G., Bullock, A.T. (1982). Spin Label and Spin Probe Studies of Synthetic Polymers. In: Dawkins, J.V. (eds) Developments in Polymer Characterisation—3. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-7346-6_4
Download citation
DOI: https://doi.org/10.1007/978-94-009-7346-6_4
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-009-7348-0
Online ISBN: 978-94-009-7346-6
eBook Packages: Springer Book Archive