Pulsed High-Frequency EPR

  • Thomas F. Prisner
Part of the Biological Magnetic Resonance book series (BIMR, volume 22)


Pulsed high-field / high-frequency EPR offers the possibility to detect coherences and relaxation properties in disordered samples in much detail. The reason is the spectrally resolved G-tensor, which allows to obtain orientation dependent information even in disordered samples, like proteins. The use of the typical pulsed EPR measurements at high magnetic fields will be discussed and application examples will be given.

Key words

Pulsed EPR Librational motion Transverse Relaxation Anisotropic rotational motion Field-swept EPR. 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Bartoschek, S., Johansson M., Geierstanger B.H., Okun J.G., Lancester C.R.D., Humpfer E., Yu C.A., Griesinger C., Brandt U., 2001, Three ubiquinone molecules essential forenergy conservatin by respiratory cytochrome bci complex, J. Biol. Chem. 276: 35231–35234PubMedCrossRefGoogle Scholar
  2. Becerra, L.R., Gerfen, G.J., Bellew, B.F., Bryant, J.A., Hall D.A., Inati, S..J.,Weber, R.T., Un, S., Prisner, T.F., McDermott, A.E., Fishbein, K.W., Kreischer, K.E., Temkin, R.J., Singel, D.J., and Griffin, R.G., 1995, A Spectrometer for Dynamic Nuclear Polarization and Electron Paramagnetic Resonance at High Frequencies, J. Magn. Res. A117:28–40.Google Scholar
  3. Bennati, M., Farrar, C.T., Bryant, J.A., Inati, S.J., Weis, V., Gerfen, G.J., Riggs-Gelasco, P., Stubbe, J., Griffin, R.G., 1999, Pulsed Electron-Nuclear Double Resonance (ENDOR) at 140 GHz, J.Magn.Res. 138: 232–243.CrossRefGoogle Scholar
  4. Bittl, R. and Zech, S.G., 1997, Pulsed EPR Study of Spin-Coupled Radical Pairs in Photosynthetic Reaction Centers: Measurements of the Distance Between P700 and Al in Photosystem I and between P865 and QA in Bacterial Reaction Centers, J. Phys. Chem. B 101: 1429–1436.CrossRefGoogle Scholar
  5. Bloeß, A., Möbius, K., and Prisner, T.F., 1998, High-Frequency/High-Field Electron Spin Echo Envelope Modulation Study of Nitrogen Hyperfine and Quadrupole Interactions on a Disordered Powder Sample, J. Magn. Res. 134: 30–35.CrossRefGoogle Scholar
  6. Bowman, M., and Kevan, L., 1979, Time Domain Electron Spin Resonance (Kevan, L and Schwartz, R.N., eds.) ( Wiley, New York).Google Scholar
  7. Bresgunov, A.Yu., Dubinskii, A.A., Krimov, V.N., Petrov, Yu.G., Poluektov, O.G., and Lebedev, Ya.S., 1991, Pulsed EPR in 2-mm Band, Appl. Magn. Res. 2: 715–728.CrossRefGoogle Scholar
  8. Breton, J, and Naberdryk, E., 1995, Protein and Bacteriopheophytin Response to QA Reduction in Photosynthetic Bacterial Reaction Centers from RB. Sphaeroides andGoogle Scholar
  9. RB. Viridis Investigated by 1H/2H Exchange and Light-induced FTIR Difference Spectroscopy, Vol. I:395–400, Photosyntesis: From Light to Biosphere (Mathis, P., ed.) (Kluwer Acad. Publ.).Google Scholar
  10. Budil, D.E., Earle, K.A., Lynch, B., and Freed, J., 1989, Electron Paramagnetic Resonance at 1 Millimeter Wavelengths, Advanced EPR in Biology and Biochemistry (Hoff, A.J., ed.), ( Elsevier, Amsterdam).Google Scholar
  11. Budil, D.E., Earle, K.A., and Freed, J.H., 1993, Full determination of the rotational diffusion tensor by electron paramagnetic Resonance at 250 GHz, J. Phys. Chem., 97: 1294.CrossRefGoogle Scholar
  12. Burghaus, 0., Rohrer, M., Götzinger, T., Plato, M., and Möbius, K., 1992, A novel highfield/high-frequency EPR and ENDOR spectrometer operating at 3mm wavelength, Meas. Sci. Technol. 3: 765.Google Scholar
  13. Burghaus, 0., Plato, M., Rohrer, M., Möbius, K., MacMillan, F., and Lubitz, W., 1993, 3mm High-Field EPR on Semiquinone Radical Anions Q Related to Photosynthesis and on the Primary Donor P and Acceptor QA in Reaction Centers of Rhodobacter sphaeroides R-26, J. Phys. Chem. 97: 7639–7647.Google Scholar
  14. Coremans, J.W.A., Poluektov, O.G., Groenen, E.J.J., Canters, G.W., Nar, H., and Messerschmidt, A., 1996, A W-Band Electron Nuclear Double Resonance Study of Single Crystals of 14N and 15N Azurin, J. Am. Chem. Soc. 118: 12141–12153.CrossRefGoogle Scholar
  15. Coremans, J.W.A., Poluektov, O.G., Groenen, E.J.J., Canters, G.W., Nar, H., and Messerschmidt, A., 1997, A W-Band Electron Spin Echo Envelope Modulation Study of a Single Crystal of Azurin, J. Am. Chem. Soc. 119: 4726–4731.CrossRefGoogle Scholar
  16. Dinse, K.-P., 2000, FT-EPR and Pulsed ENDOR Studies of Encapsulated Atoms and Ions, Electron Paramagnetic Resonance 17, 78–108.CrossRefGoogle Scholar
  17. Disselhorst, J.A.J.M., van der Meer, H., Poluektov, O.G., and Schmidt, J., 1995, A Pulsed EPR and ENDOR Spectrometer Operating at 95 GHz, J. Magn. Res. A 115: 183–188.CrossRefGoogle Scholar
  18. Dobbert, 0., Prisner, T., and Dinse, K.P., 1986, Single-Channel Quadrature FT ESR, J. Magn. Res. 70: 173–175.Google Scholar
  19. Dzuba, S.A., Kodera, Y., Hara, H., and Kawamori, A., 1993, The Use of Selective Hole Burning in EPR Spectra to Study Spectral Diffusion and Dipolar Broadening, J. Magn. Res. A 102: 257–260.Google Scholar
  20. Earle, K.A., Budil, D.E., Freed, J.H., 1993, 250-GHz EPR of Nitroxides in the Slow-Motional Regime: Models of Rotational Diffusion, J. Phys. Chem. 97: 13289.Google Scholar
  21. Earle, K.A., Budil, D.E., Freed, J.H., 1996, Millimeter Wave Electron Resonance using Quasioptical Techniques, Vol 19, Advances in Magnetic and Optical Resonance (Warren, W. ed., Academic Press ) 253–323.Google Scholar
  22. Earle, K.A.,Tipikin, D., and Freed, J.H., 1996, Far-infrared electron-paramagneticresonance spectrometer utilizing a quasioptical bridge, Rev. Sci Instrum. 67: 2502–2513.Google Scholar
  23. Epel, B and Goldfarb, D., 2000, Two-Dimensional Pulsed TRIPLE at 95 GHz, J.Magn.Res. 146: 196–203.CrossRefGoogle Scholar
  24. Ernst, R.R., 1970, Magnetic Resonance with Stochastic Excitation, J.Magn.Reson. 3: 10.Google Scholar
  25. Fritzsch, G., Ermler, U., and Michel, H., 1995, The water chains around QA and QB and other structural aspects of the reaction centre from RB. sphaeroides, Vol. I, Photosyntesis: From Light to Biosphere ( Mathis, P., ed.) (Kluwer Acad. Publ. ) 599–602.Google Scholar
  26. Fuhs, M., Prisner, T.F. and Möbius, K., 2001, Fourier-Transform EPR at HighField/High-Frequency (3.4T/95 GHz) Using Broadband Stochastic Microwave Excitation, J.Magn.Res. 149: 67–73.CrossRefGoogle Scholar
  27. Gorcester, J., Millhauser, G.L., and Freed, J.H., 1989, Two Dimensional and Fourier Transform EPR, Advanced EPR in Biology and Biochemistry (Hoff, A.J. ed.), ( Elsevier, Amsterdam).Google Scholar
  28. Gorcester, J. and Freed, J.H., 1986, Two-Dimensional Fourier Transform ESR Spectroscopy, J. Chem. Phys. 85: 5375CrossRefGoogle Scholar
  29. Grimaldi, S., MacMillan, F., Ostermann, T., Ludwig, B. Michel, H., and Prisner, T., 2001, QH.- Ubisemiquinone Radical in the b03-Type Ubiquinol Oxidase Studied by Pulsed Electron Paramagnetic Resonance and Hyperfine Sublevel Correlation Spectroscopy, Biochemistry 40: 1037–1043.Google Scholar
  30. Gromov, I., Krymov, V., Manikandan, P., Arieli, D., Goldfarb, D., 1999, A W-Band Pulsed ENDOR Spectrometer: Setup and Application to Transition Metal Centers, J.Magn.Res. 139: 8–17.CrossRefGoogle Scholar
  31. Hornak, J.P. and Freed, J.H., 1986, Spectral Rotation in Pulsed ESR Spectroscopy, J.Magn.Res. 67: 501–518.Google Scholar
  32. Höfer, P., Maresch, G.G., Schmalbein, D., Holczer, K., 1996, Bruker Rep. 142: 15–21.Google Scholar
  33. Höfer, P., Grupp, A., Mehring, M., 1986, High-resolution time-domain electron-nuclear-sublevel spectroscopy by pulsed coherence transfer, Phys.Rev. 33: 3519–3522.Google Scholar
  34. Jeschke, G., Rakhmatullin, R., and Schweiger, A., 1998, Sensitivity Enhancement byGoogle Scholar
  35. Matched Microwave Pulses in One-and Two-Dimensional Electron Spin Echo Envelope Modulation Spectroscopy, J. Magn. Res. 131:261–271.Google Scholar
  36. Jeschke, G. and Spiess, H.W., 1998, NMR-Correlated High-Field Electron Paramagnetic Resonance Spectroscopy, Chem. Phys. Lett., 293: 9.CrossRefGoogle Scholar
  37. Kababya, S., Luz, Z., and Goldfarb, D., 1994, Chemical and Heisenberg Exchange in Ion-Paix Solutions Revisited by Two-Dimensional EPR Spectroscopy, J.Am.Chem.Soc. 116: 5805.CrossRefGoogle Scholar
  38. Kaiser, R., 1970, Coherent Spectrometry with Noise Signals, J. Magn. Res., 3:28–43. Knüpling, M., Törring, J.T., and Un, S., 1997, The Realtionship between the Molecular Structure of Semiquinone Radicals and their g-Values, Chem. Phys. 219: 291–304.Google Scholar
  39. Kutter, C., Moll, H.P., van Tol, J., Zuckermann, H., Maan, J.C., and Wyder, P., 1995, Electron-Spin Echoes at 604 GHz Using Far Infrared Lasers, Phys. Rev. Lett. 74: 2925–2928.PubMedCrossRefGoogle Scholar
  40. Lubitz, W. and Feller, G., 1999, The Primary and Secondary Acceptors in Bacterial Photosynthesis III. Characterization of the Quinone Q°A- and Q°B- by EPR and ENDOR, Appl. Magn. Res. 17: 1–48.CrossRefGoogle Scholar
  41. Milov, A.D., Ponomarev, A.B., and Tsvetkov, Yu.D., 1984, Electron-Electron Double Resonance in Electron Spin Echo: Model Biradical Systems and the Sensitized Photolysis of Decalin, Chem. Phys. Lett. 110: 67–72.CrossRefGoogle Scholar
  42. Millauser, G.L. and Freed, J.H., 1984, Two-dimensional electron spin echo spectroscopy and slow motion, J. Chem. Phys. 81: 37–48.CrossRefGoogle Scholar
  43. Mims, W.B., 1972, Envelope Modulation in Spin-Echo Experiments, Phys.Rev B 5: 2409–2419.CrossRefGoogle Scholar
  44. Mims, W.B., 1972, Electron Spin Echos, Electron Paramagnetic Resonance (Geschwind, S. ed.) ( Plemum Press, N.Y.-London).Google Scholar
  45. Moll, H.P., Kutter, C., van Tol, J., Zuckermann, H. and Wyder, P., 1999, Principles and Performance of an Electron Spin Echo Spectrometer Using Far Infrared Lasers as Excitation Sources, J. Mang. Res. 137: 46–58.Google Scholar
  46. Möbius, K., 1993, High-Field EPR and ENDOR on Bioorganic Systems, Vol. 13, Biological Magnetic Resonance (Berliner, L.J. and Reuben, J. eds.) ( Plenum Press, New York).Google Scholar
  47. Muller, F., Hopkins, M.A., Coron, N., Grynberg, M., Brunel, L.C., Martinez, G., 1989, A high magnetic field EPR spectrometer, Rev. Sci. Instrum. 60: 3681–3684.CrossRefGoogle Scholar
  48. Poluektov, O.G., Donckers, M.C.J.M., Baranov, P.G., and Schmidt, J., 1993, Dynamical Properties of the Self-Trapped Exciton in AgC1 as Studied by Time-Resolved EPR at 95 GHz, Phys. Rev. B47: 10226.CrossRefGoogle Scholar
  49. Plüschau, M. and Dinse, K.-P., 1994, 2D EPR Study of a Photoinduced Proton Abstraction in the System Anthraquinone and 4-Methy1–2,6-di-tert-butylphenol in 2-Propanol, J. Magn.Res., A 109: 181–191.Google Scholar
  50. Prisner, T., Dobbert, O., and Dinse, K.P., van Willigen, H., 1988, FT ESR Study of Photoinduced Electron Transfer, J. Am. Chem. Soc. 110: 1622–1623.Google Scholar
  51. Prisner, T.F. and Dinse, K.P., 1989, ESR with Stochastic Excitation, J.Magn.Res. 84: 296–308.Google Scholar
  52. Prisner, T. F., 1996 Chapter 8 in Advances in Magnetic and Optical Resonance Vol. 13, ( Warren W., ed. ), ( Academic Press ).Google Scholar
  53. Prisner, T.F., 2001, New Methods in Electron Paramagnetic Resonance Spectroscopy for Structure and Function Determination in Biological Systems, Essay in Contemporary Chemistry.Google Scholar
  54. Prisner, T.F., 1997, Pulsed High-Frequency/High-Field EPR, Adv. Magn.Opt., 20: 245300.Google Scholar
  55. Prisner, T.F., Rohrer, M., and Möbius, K., 1994, Pulsed 95 GHz High-Field EPR Heterodyne Spectrometer with High Spectral and Time Resolution, Appl. Magn. Res. 7: 167–183.CrossRefGoogle Scholar
  56. Prisner, T.F., van der Est, A., Bittl., R., Lubitz, W., Stehlik, D., Möbius, K., 1995, Time-resolved W-band (95 GHz) EPR spectroscopy of Zn-substituted reaction centers of Rhodobacter sphaeroides R-26, Chem. Phys. 194: 361–370.Google Scholar
  57. Prisner, T.F., Un, S., and Griffin, R.G., 1992, Pulsed ESR at 140 GHz, Isr. J. Chem. 32: 357–363.Google Scholar
  58. Prisner, T.F., Rohrer, M., MacMillan, F., 2001, Pulsed EPR Spectroscopy: Biological Applications, Annu. Rev. Phys. Chem. 52: 279–313.PubMedCrossRefGoogle Scholar
  59. Rohrer, M., Gast, P., Möbius, K., Prisner, T.F., 1996, Anisotropic motion of semiquinones in photosynthetic reaction centers of Rhodobacter sphaeroides R26 and in frozen isopropanol solution as measured by pulsed high-field EPR at 95 GHz, Chem. Phys. Lett. 259: 523–530.CrossRefGoogle Scholar
  60. Rohrer, M., Brügmann, O., Kinzer, B., and Primer, T.F., 2001, High-Field/HighFrequency EPR Spectrometer Operating in Pulsed and Continuous-Wave Mode at 180 GHz, Appl. Magn. Res. 21: 257–274.CrossRefGoogle Scholar
  61. Rohrer, M., Prisner, T.F., Brügmann, O., Kass, H., Spoemer, M., Wittinghofer, A., and Kalbitzer, H.R., 2001, Structure of the Metal-Water Complex in Ras•GDP Studied by High-Field EPR Spectroscopy and 31 P NMR Spectroscopy, Biochemistry, 40: 1884–1889.PubMedCrossRefGoogle Scholar
  62. Saxena, S., Freed, J.H., 1996, Double quantum two-dimensional Fourier transform electron spin resonance: distance measurements, Chem.Phys. Letters 251: 102–110.CrossRefGoogle Scholar
  63. Saxena, S. and Freed, J.H., 1997, Two-Dimensional Electron Spin Resonance and Slow Motions, J.Phys. Chem. A101: 7998.CrossRefGoogle Scholar
  64. Schnegg, A., Fuhs, M., Rohrer, M., Lubitz, W., Prisner, T.F., and Möbius, K., 2002, Molecular Dynamics of QA and QB“ in Photosynthetic Bacterial Reaction Centers Studied by Pulsed High-Field EPR at 95 GHz, J. Phys. Chem. B 106: 9454–9462CrossRefGoogle Scholar
  65. Schweiger, A., 1991, Pulsed Electron Spin Resonance Spectroscopy: Basic Principles, Techniques, and Examples of Applications, Angew.Chem.Int.Ed.Engl. 30: 265–292.CrossRefGoogle Scholar
  66. Schweiger, A. and Jeschke, G., 2001, Principles of pulse electron paramagnetic resonance Google Scholar
  67. Stehlik, D. and Möbius, K., 1997, New EPR Methods for Investigating Photoprocesses with Paramagnetic Intermediates, Annu. Rev. Phys. Chem. 48: 739–778.CrossRefGoogle Scholar
  68. Stoll, S., Jeschke, G., Willer, M., and Schweiger, A., 1998, Nutation-Frequency Correlation EPR Spectroscopy: The PEANUT Experiment, J.Magn.Res. 130: 86–96.CrossRefGoogle Scholar
  69. Wacker, Th. and Schweiger, A., 1991, Chem.Phys.Lett. 186: 27.CrossRefGoogle Scholar
  70. Weber, R.T., Disselhorst, J.A.J.M., Prevo, L.J., Schmidt, J., and Wenckebach, W.Th., 1989, Electron Spin-Echo Spectroscopy at 95 GHz, J.Magn.Res. 81: 129–144.Google Scholar
  71. Willer, M. and Schweiger, A., 1994, Forbidden-transition-labelled EPR (FORTE). An approach for the sensitive measurement of forbidden EPR transitions, Chem.Phys.Lett. 230: 67.CrossRefGoogle Scholar
  72. Zech, S.G., Bittl, R., Gardiner, A.T., and Lubitz, W., 1997, Transient and Pulsed EPR Spectroscopy on the Radical Pair State P865 +*-QA * to Study Light-Induced Changes in Bacterial Reaction Centers, Appl. Magn. Res., 13: 517–529.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2004

Authors and Affiliations

  • Thomas F. Prisner
    • 1
  1. 1.Institute of Physical and Theoretical Chemistry,Center of Biological Magnetic ResonanceGoetheGoethe University FrankfurtFrankfurtGermany

Personalised recommendations