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Absolute signs of hyperfine coupling constants as determined by pulse ENDOR of polarized radical pairs

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Abstract

A novel method that allows the determination of absolute signs of hyperfine coupling constants in polarized radical pair (RP) pulse electron-nuclear double resonance (ENDOR) spectra is presented, The variable mixing time (VMT) ENDOR method used here leads to a separation of ENDOR transitions originating from different electron spin manifolds by employing their dependence on the time-dependent parameters of the pulse sequence. The simple kinetic model of the RP VMT ENDOR experiment shows very good agreement with the experiments performed on the P .+700 A .-1 RP in photosystem I. This method relies on the selective excitation of absorptive or emissive lines of one radical in the RP EPR spectrum and therefore requires high spectral resolution. This condition was fulfilled for the system studied at the low-field edge of the RP EPR spectrum obtained at Q-band. The method presented here has a very high sensitivity and does not require any equipment additional to the one used for RP pulse ENDOR. The VMT ENDOR method offers the possibility for selective suppression of signals from different electron spin manifolds.

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References

  1. Feher G.: Phys. Rev.103, 834–835 (1956)

    Article  ADS  Google Scholar 

  2. Möbius K., Plato M., Lubitz W.: Phys. Rep.87, 171–208 (1982)

    Article  ADS  Google Scholar 

  3. Kurreck H., Kirste B., Lubitz W.: Electron Nuclear Double Resonance Spectroscopy of Radicals in Solution: Applications to Organic and Biological Chemistry. New York: VCH 1988.

    Google Scholar 

  4. Schweiger A., Jeschke G.: Principles of Pulse Electron Paramagnetic Resonance. New York: Oxford University Press 2001.

    Google Scholar 

  5. Lubitz W. in: Electron Paramagnetic Resonance, vol. 19, pp. 174–242. Specialist Periodical Reports. Cambridge: Royal Society of Chemistry 2004.

    Book  Google Scholar 

  6. Bittl R., Zech S.G., Teutloff C., Krabben L., Lubitz W. in: Photosynthesis: Mechanisms and Effects (Garab G., ed.), pp. 509–514. Dordrecht: Kluwer Academic 1998.

    Google Scholar 

  7. Bittl R., Zech S.G.: Biochim. Biophys. Acta1507, 194–211 (2001)

    Article  Google Scholar 

  8. Fursman C.E., Teutloff C., Bittl R.: J. Phys. Chem. B106, 9679–9686 (2002)

    Article  Google Scholar 

  9. Teutloff C., Bittl R., Lubitz W.: Appl. Magn. Reson.26, 5–21 (2004)

    Article  Google Scholar 

  10. Poluektov O.G., Utschig L.M., Dubinskij A.A., Thurnauer M.C.: J. Am. Chem. Soc.126, 1644–1645 (2004)

    Article  Google Scholar 

  11. Carrington A., McLachlan A.D.: Introduction to Magnetic Resonance with Applications to Chemistry and Chemical Physics. New York: Harper & Row 1969.

    Google Scholar 

  12. Gerson F., Huber W.: Electron Spin Resonance Spectroscopy of Organic Radicals. New York: Wiley InterScience 2003.

    Book  Google Scholar 

  13. Cook R.J., Whiffen D.H.: Proc. Phys. Soc. London84, 845–848 (1964)

    Article  Google Scholar 

  14. Biehl R., Plato M., Möbius K.: J. Chem. Phys.63, 3515–3522 (1975)

    Article  ADS  Google Scholar 

  15. Mehring M., Höfer P., Grupp A.: Ber. Bunsen-Ges. Phys. Chem.91, 1132–1137 (1987)

    Google Scholar 

  16. Epel B., Goldfarb D.: J. Magn. Reson.146, 196–203 (2000)

    Article  ADS  Google Scholar 

  17. Möbius K., Lubitz W., Plato M. in: Advanced EPR: Applications in Biology and Biochemistry (Hoff A.J., ed.), pp. 441–499. Amsterdam: Elsevier 1989.

    Google Scholar 

  18. Epel B., Pöppl A., Manikandan P., Vega S., Goldfarb D.: J. Magn. Reson.148, 388–397 (2001)

    Article  ADS  Google Scholar 

  19. Epel B., Manikandan P., Kroneck P.M.H., Goldfarb D.: Appl. Magn. Reson.21, 287–297 (2001)

    Article  Google Scholar 

  20. Davies E.R.: Phys. Lett. A47, 1–2 (1974)

    Article  ADS  Google Scholar 

  21. Thurnauer M.C., Brown J.W., Gast P., Feezel L.L.: Radiat. Phys. Chem.34, 647–651 (1989)

    Google Scholar 

  22. Bock C.H., Van der Est A., Brettel K., Stehlik D.: FEBS Lett.247, 91–96 (1989)

    Article  Google Scholar 

  23. Jordan P., Fromme P., Witt H.T., Klukas O., Saenger W., Krauss N.: Nature411, 909–917 (2001)

    Article  ADS  Google Scholar 

  24. Fromme P., Witt H.T.: Biochim. Biophys. Acta1365, 175–184 (1998)

    Article  Google Scholar 

  25. Sienkiewicz A., Smith B.G., Veselov A., Scholes C.P.: Rev. Sci. Instrum.67, 2134–2138 (1996)

    Article  ADS  Google Scholar 

  26. Epel B., Gromov I., Stoll S., Schweiger A., Goldfarb D.: Concepts Magn. Reson. B26, 36–45 (2005)

    Article  Google Scholar 

  27. Salikhov K.M., Schlüpmann J., Plato M., Möbius K.: Chem. Phys.215, 23–35 (1997)

    Article  Google Scholar 

  28. Kandrashkin Y.E., Salikhov K.M., Van der Est A., Stehlik D.: Appl. Magn. Reson.15, 417–447 (1998)

    Article  Google Scholar 

  29. Hore P.J. in: Advanced EPR: Applications in Biology and Biochemistry (Hoff A.J., ed.), pp. 405–440. Amsterdam: Elsevier 1989.

    Google Scholar 

  30. Buckley C.D., Hunter D.A., Hore P.J., McLauchlan K.A.: Chem. Phys. Lett.135, 307–312 (1987)

    Article  ADS  Google Scholar 

  31. Closs G.L., Forbes M.D.E., Norris J.R.: J. Phys. Chem.91, 3592–3599 (1987)

    Article  Google Scholar 

  32. Hore P.J., Hunter D.A., McKie C.D., Hoff A.J.: Chem. Phys. Lett.137, 495–500 (1987)

    Article  ADS  Google Scholar 

  33. Bittl R., Kothe G.: Chem. Phys. Lett.177, 547–553 (1991)

    Article  ADS  Google Scholar 

  34. Kothe G., Weber S., Bittl R., Ohmes E., Thurnauer M.C., Norris J.R.: Chem. Phys. Lett.186, 474–480 (1991)

    Article  ADS  Google Scholar 

  35. Dzuba S.A., Bosch M.K., Hoff A.J.: Chem. Phys. Lett.248, 427–433 (1996)

    Article  ADS  Google Scholar 

  36. Timmel C.R., Fursman C.E., Hoff A.J., Hore P.J.: Chem. Phys.226, 271–283 (1998)

    Article  Google Scholar 

  37. Zech S., Hofbauer W., Kamlowski A., Fromme P., Stehlik D., Lubitz W., Bittl R.: J. Phys. Chem. B104, 9728–9739 (2000)

    Article  Google Scholar 

  38. Rigby S.E.J., Evans M.C.W., Heathcote P.: Biochim. Biophys. Acta1507, 247–259 (2001)

    Article  Google Scholar 

  39. Poluektov O.G., Utschig L.M., Dubinskij A.A., Thurnauer M.C.: J. Am. Chem. Soc.127, 4049–4059 (2005)

    Article  Google Scholar 

  40. Salikhov K.M., Molin Y.N.: J. Phys. Chem.97, 13259–13266 (1993)

    Article  Google Scholar 

  41. Iwaki M., Itoh S., Hara H., Kawamori A.: J. Phys. Chem. B102, 10440–10445 (1998)

    Article  Google Scholar 

  42. Dzuba S.A., Hara H., Kawamori A., Iwaki M., Itoh S., Tsvetkov Y.D.: Chem. Phys. Lett.264, 238–244 (1997)

    Article  ADS  Google Scholar 

  43. Dzuba S.A., Proskuryakov I.I., Hulsebosch R.J., Bosch M.K., Gast P., Hoff A.J.: Chem. Phys. Lett.253, 361–366 (1996)

    Article  ADS  Google Scholar 

  44. Dzuba S.A., Kawamori A., Katsuta N., Hara H., Mino H., Itoh S.: Chem. Phys. Lett.362, 307–313 (2002)

    Article  ADS  Google Scholar 

  45. Brettel K.: Biochim. Biophys. Acta1318, 322–373 (1997)

    Article  Google Scholar 

  46. Brettel K., Leibl W.: Biochim. Biophys. Acta1507, 100–114 (2001)

    Article  Google Scholar 

  47. Epel B., Niklas J., Sinnecker S., Zimmerman H., Lubitz W.: J. Phys. Chem. B110, 11549–11560 (2006)

    Article  Google Scholar 

  48. Stehlik D., Möbius K.: Annu. Rev. Phys. Chem.48, 745–784 (1997)

    Article  Google Scholar 

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Author notes

  1. M. L. Antonkine

    Present address: Photochemistry Center, Russian Academy of Sciences, Moscow, Russian Federation

Authors and Affiliations

  1. Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470, Mülheim and der Ruhr, Germany

    B. Epel, J. Niklas, M. L. Antonkine & W. Lubitz

  2. Institut für Experimentalphysik, Freie Universität Berlin, Berlin, Germany

    M. L. Antonkine

Authors
  1. B. Epel
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  2. J. Niklas
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  3. M. L. Antonkine
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  4. W. Lubitz
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Epel, B., Niklas, J., Antonkine, M.L. et al. Absolute signs of hyperfine coupling constants as determined by pulse ENDOR of polarized radical pairs. Appl. Magn. Reson. 30, 311–327 (2006). https://doi.org/10.1007/BF03166203

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  • DOI: https://doi.org/10.1007/BF03166203

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