Abstract
Four biradicals of differing chain lengths have been prepared by spin-labelling the sulphhydryl groups of dithiothreitol. Temperature-dependent EPR spectra of these biradicals indicate that the dynamics of biradicals is associated with both fast and slow exchanges of conformations. The three-conformational model incorporating cage configuration is found to be more appropriate. Certain thermodynamic parameters of conformationalchanges have been calculated from the experimental EPR parameters, obtained by the use of simulation procedures developed recently.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Alinger N L 1977J. Am. Chem. Soc. 99 8127
Buchachencko A L and Vasserman A M 1973The stable radicals (Moscow: Khimiya)
Calvin M, Wang H H, Entine G, Gill D, Ferruti P, Harpold M A and Klein M P 1969Proc. Natl. Acad. Sci. USA 1 63
Ferruti P, Gill D, Klein M P and Calvin M 1969J. Am. Chem. Soc. 91 7765
Ferruti P, Gill D, Klein M P, Wang H H, Entine G and Calvin M 1970J. Am. Chem. Soc. 92 3704
Johnson C S Jr 1965Adv. Magn. Resort. 1 33
Kaplan J I 1958J. Chem. Phys. 28 278
Kokorin AI and Parmon V N 1978Izv. Akad. Nauk SSSR, Ser. Khim. 13 576; 1978Chem. Abstr. 89 107767v
Luckhurst G R 1966Mol. Phys. 10 543
Luckhurst G R and Pedulli G F 1970Mol. Phys. 92 4738
Metzner E K, Libertini L J and Calvin M 1974J. Am. Chem. Soc. 96 6515
Metzner E K, Libertini L J and Calvin M 1977J. Am. Chem. Soc. 99 4500
Molin Yu N, Salikov K M and Zamaraev K I 1980Spin exchange (Berlin: Springer-Verlag)
Parmon V N, Kokorin A I and Zamaraev K I 1976Izv. Akad. Nauk SSSR, Ser. Khim. 8 1776; 1976Chem. Abstr. 86 4422n
Parmon V N, Kokorin A I and Zhidomirov G M 1977Zh. Strukt. Khim. 18 104
Parmon V N, Kokorin A I, Zhidomirov G M and Zamaraev K I 1975Mol. Phys. 30 695
Parmon V N and Zhidomirov G M 1974Mol. Phys. 27 367
Parmon V N and Zhidomirov G M 1976Mol. Phys. 32 613
Rabinowitch E 1937Trans. Faraday Soc. 33 1225
Sankarapandi S, Chandramouli G V R, Daul C and Manoharan P T 1993J. Magn. Reson. A103 163
Sankarapandi S, Sukumar R, Balaram P and Manoharan P T 1994 (to be published)
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Sankarapandi, S., Rifkind, J.M. & Manoharan, P.T. Thermodynamics of some long-chain biradicals studied by EPR spectroscopy. Proc. Indian Acad. Sci. (Chem. Sci.) 106, 1329–1340 (1994). https://doi.org/10.1007/BF02840690
Issue Date:
DOI: https://doi.org/10.1007/BF02840690