Skip to main content
SpringerLink
Log in

Nitroxide Diradical EPR Lineshapes and Spin Relaxation

  • Original Paper
  • Published:
Applied Magnetic Resonance Aims and scope Submit manuscript

Abstract

EPR line shapes in fluid solution and electron spin relaxation times and lineshapes in frozen solution were measured at X-band for two dinitroxides. For dinitroxide 1, which has two proxyl nitroxides connected by an amide linkage, the fluid solution spectra are in the strong exchange limit (J >> nitrogen hyperfine coupling) and the interspin distance in glassy water:glycerol is about 8.8 Å. For dinitroxide 2, which has two proxyl nitroxides connected by a bridging ethylenediamine and two amide linkages, the fluid solution spectra are characteristic of dynamic exchange between conformations with strong exchange (J > 850 MHz) and conformations with weaker exchange interaction. For 2, the interspin distance in glassy water:glycerol is about 9.2 Å and J > 600 MHz. T1 and Tm for both dinitroxides in 1:1 water:glycerol were measured at 10 to 160 K. Relaxation times are within experimental uncertainty of values for a pyrrolinoxyl monoradical and very similar to values for a nitroxide with a piperidinyl ring. These data demonstrate that even for these relatively flexible linkages dipolar interaction with an interspin distance of about 9 Å does not provide an effective spin–lattice relaxation mechanism for dinitroxides in glassy water:glycerol.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. E.G. Rozantsev, Free Nitroxyl Radicals (Plenum Press, New York, 1970)

    Book  Google Scholar 

  2. S.S. Eaton, L.B. Woodcock, G.R. Eaton, Conc. Magn. Reson. A (2018). https://doi.org/10.1002/cmr.a.21246

    Article  Google Scholar 

  3. B.M. Sawant, G.R. Eaton, S.S. Eaton, J. Magn. Reson. 45, 162–169 (1981)

    ADS  Google Scholar 

  4. D.J. Kubicki, G. Casano, M. Schwarzwalder, S. Abel, C. Sauvee, K. Ganesan, M. Yulikov, A.J. Rossini, G. Jeschke, C. Coperet, A. Lesage, P. Tordo, O. Ouari, L. Emsley, Chem. Sci. 7, 550–558 (2016)

    Article  Google Scholar 

  5. G.I. Roshchupkina, A.A. Bobko, A. Bratasz, V.A. Reznikov, P. Kuppusamy, V.V. Khramtsov, Free Rad. Biol Med. 45, 312–320 (2008)

    Article  Google Scholar 

  6. E.A. Legenzov, S. Muralidharan, L.B. Woodcock, G.R. Eaton, S.S. Eaton, G.M. Rosen, J.P.Y. Kao, Bioconj. Chem. 27, 2923–2930 (2016)

    Article  Google Scholar 

  7. B. Epel, S.V. Sundramoorthy, M. Krzykowska-Serda, M.C. Maggio, M. Tseytlin, G.R. Eaton, S.S. Eaton, G.M. Rosen, J.P.Y. Kao, H.J. Halpern, J. Magn. Reson. 276, 31–36 (2017)

    Article  ADS  Google Scholar 

  8. G. Jeschke, Annu. Rev. Phys. Chem. 63, 419–446 (2012)

    Article  ADS  Google Scholar 

  9. Y.D. Tsvetkov, M.K. Bowman, Y.A. Grishin, Pulsed Electron-Electron Double Resonance (Springer International Publishing, Switzerland, 2019)

    Book  Google Scholar 

  10. S.S. Eaton, G.R. Eaton, in Distance Measurements in Biological Systems by EPR. ed. by L.J. Berliner, G.R. Eaton, S.S. Eaton (Springer US, Boston, 2000), pp. 29–154

    Google Scholar 

  11. A.N.A. Zecevic, G.R. Eaton, S.S. Eaton, M. Lindgren, Mol. Phys. 95(6), 1255–1263 (1998)

    Article  ADS  Google Scholar 

  12. H. Sato, V. Kathirvelu, A. Fielding, J.P. Blinco, A.S. Micallef, S.E. Bottle, S.S. Eaton, G.R. Eaton, Mol. Phys. 105(15–16), 2137–2151 (2007)

    Article  ADS  Google Scholar 

  13. G.R. Luckhurst, Mol. Phys. 10(6), 543–550 (1966)

    Article  ADS  Google Scholar 

  14. S.S. Eaton, L.B. Woodcock, G.R. Eaton, Concepts Magn. Reson. Part A 47A(2), e21426 (2018)

    Article  Google Scholar 

  15. H. Sato, V. Kathirvelu, G. Spagnol, S. Rajca, S.S. Eaton, G.R. Eaton, J. Phys. Chem. B. 112, 2818–2828 (2008)

    Article  Google Scholar 

  16. R.L. Ehman, R.C. Brasch, M.T. McNamara, U.L.F. Erikkson, G. Sosnovsky, J. Luksz, S.W. Li, Invest. Radiol. 21(2), 125–131 (1986)

    Article  Google Scholar 

  17. J.S. Hyde, A. Jesmanowicz, J.J. Ratke, W.E. Antholine, J. Magn. Reson. 96(1), 1–13 (1992)

    ADS  Google Scholar 

  18. S. Stoll, A. Schweiger, J. Magn. Reson. 178, 42–55 (2006)

    Article  ADS  Google Scholar 

  19. J.R. Biller, H. Elajaili, V. Meyer, G.M. Rosen, S.S. Eaton, G.R. Eaton, J. Magn. Reson. 236, 47–56 (2013)

    Article  ADS  Google Scholar 

  20. S.S. Eaton, K.M. More, B.M. Sawant, P.M. Boymel, G.R. Eaton, J. Magn. Reson. 52(3), 435–449 (1983)

    ADS  Google Scholar 

  21. S.S. Eaton, G.R. Eaton, in EPR Spectroscopy: Fundamentals and Methods. ed. by D. Goldfarb, S. Stoll (John Wiley & Sons Ltd, Chichester, 2018), pp. 175–192

    Google Scholar 

  22. V.N. Parmon, A.I. Kokorin, G.M. Zhidomirov, Zh. Strukt. Khim. 18, 104–147 (1977). (in English translation)

    Google Scholar 

  23. I.S. Khattab, F. Bandarkar, M.A.A. Fakhree, A. Jouyban, Korean J. Chem. Eng. 29, 812–817 (2012)

    Article  Google Scholar 

  24. G.R. Luckhurst, Mol. Phys. 10, 543–550 (1966)

    Article  ADS  Google Scholar 

  25. A. Rajca, V. Kathirvelu, S.K. Roy, M. Pink, S. Rajca, S. Sarkar, S.S. Eaton, G.R. Eaton, Chem. Eur. J. 16, 5778–5782 (2010)

    Article  Google Scholar 

  26. A. Zagdoun, G. Casano, O. Ouari, G. Lapadula, A.J. Rossini, M. Lelli, M. Baffert, D. Gajan, L. Veyre, W.E. Maas, M. Rosay, R.T. Weber, C. Thieuleux, C. Coperet, A. Lesage, P. Tordo, L. Emsley, J. Am. Chem. Soc. 134, 2284–2291 (2012)

    Article  Google Scholar 

  27. A. Zagdoun, G. Casano, O. Ouari, M. Schwarzwalder, A.J. Rossini, F. Aussenac, M. Yulikov, G. Jeschke, C. Coperet, A. Lesage, P. Tordo, L. Emsley, J. Am. Chem. Soc. 135, 12790–12797 (2013)

    Article  Google Scholar 

  28. C. Sauvee, G. Casano, S. Abel, A. Rockenbauer, D. Akhmetzyanov, H. Karoui, D. Siri, F. Aussenac, W. Maas, R.T. Weber, T. Prisner, M. Rosay, P. Tordo, O. Ouari, Chem. Eur. J 22, 5598–5606 (2016)

    Article  Google Scholar 

  29. C. Sauvee, M. Rosay, G. Casano, F. Aussenac, R.T. Weber, O. Ouari, P. Tordo, Angew. Chem. Int. Ed. 52, 10858–10861 (2013)

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported in part by National Institutes of Health (R01 GM124310-01 SSE), the University of Denver, and the Nanobiology Research Fund of the University of Maryland Baltimore Foundation.

Author information

Authors and Affiliations

  1. Center for Biomedical Engineering & Technology (BioMET) and Department of Physiology, University of Maryland School of Medicine, 111 Penn Street, Baltimore, MD, 21201, USA

    Joseph P. Y. Kao, Nathaniel D. A. Dirda & Eric A. Legenzov

  2. Department of Chemistry and Biochemistry, University of Denver, Denver, CO, 80210, USA

    Whylder Moore, Lukas B. Woodcock, Sandra S. Eaton & Gareth R. Eaton

Authors
  1. Joseph P. Y. Kao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Whylder Moore
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Lukas B. Woodcock
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nathaniel D. A. Dirda
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Eric A. Legenzov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sandra S. Eaton
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Gareth R. Eaton
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Joseph P. Y. Kao.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kao, J.P.Y., Moore, W., Woodcock, L.B. et al. Nitroxide Diradical EPR Lineshapes and Spin Relaxation. Appl Magn Reson 53, 221–232 (2022). https://doi.org/10.1007/s00723-021-01372-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00723-021-01372-9

Search

Navigation