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Distance Measurements in Biological Systems by EPR pp 569–596Cite as

Photo-Induced Radical Pairs Investigated Using Out-Of-Phase Electron Spin Echo

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Part of the book series: Biological Magnetic Resonance ((BIMR,volume 19))

Abstract

Electron spin echo experiment on photo-induced radical pairs in photosynthetic reaction centers produces the echo signal which is out-of-phase due to spin coherence. This signal is strongly modulated because of the electron spin-spin dipolar and exchange couplings in the pair. Fourier transformation of the time-domain modulation produces a “Pake doublet” from the two coupled spins, which allows the accurate determination of the distance between the two radicals. The precision with which the distance can be measured is 0.3 – 0.4 Å, for radicals separated in the pair by ~ 30 Å. This high precision provides a very sensitive tool for structural investigations in photosynthetic reaction centers. The method is applicable to spin-correlated radical pairs separated by 20 – 40 Å and possessing an EPR linewidth accessible for the full excitation by the microwave pulses.

This chapter is based on an earlier paper (Hoff et al., 1998) a few sections of which are reproduced with permission from Elsevier Science

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References

  • Angerhofer, A. and Bittl, R. (1996) Radicals and radical pairs in photosynthesis. Photochem. Photobiol. 63, 11–38.

    Article  CAS  Google Scholar 

  • Bittl, R. and Zech, S.G. (1997) Pulsed EPR study of spin coupled radical pairs in photosynthetic reaction centers: measurement of the distance between P700* and AI- in Photosystem I and between P865+ and QA in bacterial reaction center. J. Phys. Chem. B 101, 1429–1436.

    Article  CAS  Google Scholar 

  • Bittl, R., Zech, S.G., Fromme, P., Witt, H.T. and Lubitz, W. (1997) Pulsed EPR structure analysis of Photosystem I single crystals: localization of the phylloquinone acceptor. Biochem. 36, 12001–12004.

    Article  CAS  Google Scholar 

  • Borovykh, I.V., Dzuba, S.A., Proskuryakov, I.I., Gast P. and Hoff, A.J. (1998) Light-induced structural changes in photosynthetic reaction centers studied by ESEEM of spin-correlated D’QA radical pairs. Biochim. Biophys. Acta 1363, 182–186.

    Article  Google Scholar 

  • Chang, C.-H., El-Kabbani, O., Tiede, D., Noms J. and Schiffer M. (1991) Structure of the membrane-bound protein in photosynthetic reaction center from Rhodobacter sphaeroides. Biochemistry, 30 5352.

    Article  PubMed  CAS  Google Scholar 

  • Dikanov, S.A. and Tsvetkov, Yu.D. (1992) Electron spin echo modulation ( ESEEM) spectroscopy CRC Press, Boca Raton.

    Google Scholar 

  • Dzuba, S.A. (1997) Spin-correlated radical pairs in photosynthetic reaction centers: role of anisotropic hyperfine interaction as revealed by computational modeling. Chem. Phys. Letters 278, 333–340.

    Article  CAS  Google Scholar 

  • Dzuba, S.A., Gast P. and Hoff, A.J. (1995) ESEEM study of spin-spin interactions in spin-correlated P’QA pairs in the photosynthetic purple bacterium Rhodobacter sphaerodes R26. Chem. Phys. Letters 236, 595–602.

    Article  CAS  Google Scholar 

  • Dzuba, S.A., Bosch M.K. and Hoff, A.J. (1996) Electron spin echo detection of quantum beats and double-quantum coherence in spin-correlated radical pairs of protonated reaction centers Chem. Phys. Letters 248, 427–433.

    Article  CAS  Google Scholar 

  • Dzuba, S.A., Gast P. and Hoff, A.J. (1997a) Probing the energy landscape of bacterial photosynthetic reaction centers at cryogenic temperatures by ESEEM of spin-polarized D’QA radical pairs. Chem. Phys. Letters 268, 273–279.

    Article  CAS  Google Scholar 

  • Dzuba, S.A., Hara, H., Kawamori, A., Iwaki, M., Itoh S. and Tsvetkov, Yu.D. (1997b) Electron spin echo of spin-polarised radical pairs in intact and quinone-reconstituted plant Photosystem I reaction centers. Chem. Phys. Letters 264, 238–244.

    Article  CAS  Google Scholar 

  • Fursman, C.E. and Hore, P.J. (1999) Distance determination in spin-correlated radical pairs in photosynthetic reaction centers by electron spin echo envelope modulation. Chem. Phys. Letters 303, 593–600.

    Article  CAS  Google Scholar 

  • Hara, H., Dzuba, S.A., Kawamori, A., Akabori, K., Tomo, T., Satoh, K., Iwaki, M. and Itoh, S. (1997) The distance between P680 and QA in Photosystem II determined by ESEEM spectroscopy. Biochim. Biophys. Acta 1322, 77–85.

    Article  CAS  Google Scholar 

  • Hara, H., Tang, J., Kawamori, A., Itoh, S. and Iwaki, M. (1998) Anomalous pulse-angle and phase dependence of Harm’s electron spin echo and multiple-quantum echo of the spin-correlated radical pair P700`Af in Photosystem I. Appl. Magn. Reson. 14, 367–379.

    Article  CAS  Google Scholar 

  • Hoff, A.J., Gast, P., Dzuba, S.A., Timmel, C.R., Fursman, C.E. and Hore, P.J. (1998) The nuts and bolts of distance determination and zero and double quantum coherence in photoinduced radical pairs. Spectrochim. Acta A 54, 2283–2293.

    Article  Google Scholar 

  • Hore: P.J. (1990) Analysis of polarized electron paramagnetic resonance spectra. in: Advanced EPR, applications in biology and biochemistry,(Hoff A.J., Ed.), pp. 405–440, Elsevier, Amsterdam.

    Google Scholar 

  • Hore, P.J. (1996) Transfer of spin correlation between radical pairs in the initial steps of photosynthetic energy conversion. Mol. Phys. 89, 1195–1202.

    CAS  Google Scholar 

  • Hore, P.J., Hunter, D.A., McKie, C.D. and Hoff, A.J., (1987) Electron paramagnetic resonance of spin-correlated radical pairs in photosynthetic reactions. Chem. Phys. Letters 137, 495–500.

    Article  CAS  Google Scholar 

  • Iwaki, M., Itoh, S., Hara, H. and Kawamori, A. (1998) Spin-polarized radical pair in Photosystem I reaction center that contains different quinones and fluorenones as the secondary electron acceptor. J. Phys. Chem. B 102, 10440–10445.

    Article  CAS  Google Scholar 

  • Jeschke, G. and Bittl, R. (1998) Electron spin echo envelope modulation by electronic spin-spin interactions in radical pairs undergoing electron transfer. Chem. Phys. Letters 294, 323–331.

    Article  CAS  Google Scholar 

  • Kleinfeld, D., Okamura, M.Y. and Feher, G. (1984) Electron transfer kinetics in photosynthetic reaction centers in the charge-separated state: evidence for light-induced structural changes. Biochem. 23, 5780–5786.

    Article  CAS  Google Scholar 

  • Komiya, H., Yeates, T.O., Rees, D.C., Allen, J.P. and Feher, J. (1988) Structure of the reaction center from Rhodobacter sphaeroides R-26. Proc. Natl. Acad. Sci. US 85, 9012–9016.

    Article  CAS  Google Scholar 

  • Kothe, G., Weber, S., Bittl, R., Ohmes, E., Thumauer, M.C. and Norris, J.R., (1999) Transient EPR of light-induced radical pairs in plant photosystem I: observation of quantum beats Chem. Phys. Letters 186, 474–480.

    Article  Google Scholar 

  • Moënne-Loccoz, P., Heathcote, P., Maclachlan, D.J., Berry, M.C., Davis, I.H. and Evans, M.C.W. (1994) Path of electron transfer in photosystem I: direct evidence of forward electron transfer from Al to Fe-Ss. Biochem. 33, 10037–10042.

    Article  Google Scholar 

  • Salikhov, K.M., Kandrashkin, Yu.E. and Salikhov, A.K. (1992) Peculiarities of free induction and primary spin echo signals for spin-correlated radicals pairs, Appl. Magn. Reson. 3, 199–217.

    Article  CAS  Google Scholar 

  • Schubert, W.-D., Klukas, O., Krauss, N., Saenger, W., Fromme, P., Witt, H.T. (1997) Photosystem I of Synechococcus elongatus at 4,4 resolution: comprehensive structure analysis. J. Mol. Biol. 272, 741–769.

    Article  PubMed  CAS  Google Scholar 

  • Stowell, M.H.B., McPhillips, T.M., Rees, D.C., Soltis, S.M., Abresch, E., and Feher, G. (1997) Ligt-induced structural changes in photosynthetic reaction center: implication for mechanism of electron transfer. Science 276, 812–816.

    Article  PubMed  CAS  Google Scholar 

  • Tang, J., Thumauer, M.C. and Norris, J.R. (1994) Electron spin echo envelope modulation due to exchange and dipolar interactions in a spin-correlated radical pair. Chem. Phys. Letters 219, 283–290.

    Article  CAS  Google Scholar 

  • Tang, J. and Noms, J.R., (1995) Multiple-quantum EPR coherence in a spin-correlated radical pair system. Chem. Phys. Letters 233, 192–200.

    Article  CAS  Google Scholar 

  • Tang, J., Thumauer, M.C., Kubo, A., Hara, H. and Kawamori, A. (1997) Anomalous pulse-angle and phase dependence of Hahn’s electron spin echo and multiple-quantum echoes in a photoinduced spin-correlated radical pair. J. Chem. Phys. 106, 7471–7478.

    Article  CAS  Google Scholar 

  • Thorn Leeson, D., Wiersma, D.A., Fritsch, K. and Friedrich, J. (1997) The energy landscape of myoglobin: an optical study. J. Phys. Chem. B 101, 6331–6340.

    Article  Google Scholar 

  • Thumauer, M.C. and Norris, J.R. (1980) An electron spin echo phase shift observed in photosynthetic algae. Possible evidence for dynamic radical pair interactions. Chem. Phys. Letters 76, 557–561.

    Article  Google Scholar 

  • Timmel, C.R., Furman, C.E., Hoff A.J. and Hore, P.J. (1998) Spin-correlated radical pairs: microwave pulse effects on lifetimes, electron spin echo envelope modulations and optimum conditions for detection by electron spin echo spectroscopy. Chem. Phys. 226, 271–283.

    Article  CAS  Google Scholar 

  • Van den Brink, J.S., Hulsebosch, R.J., Gast, P., Hore, P.J. and Hoff, A.J. (1994) QA binding in reaction centers of the photosynthetic purple bacterium Rhodobacter sphaeroides R26 investigated with electron spin polarisation spectroscopy. Biochemistry 33, 13668–13677.

    Article  PubMed  Google Scholar 

  • Zech, S.G., Lubitz W. and Bittl, R. (1996) Pulsed EPR experiments on radical pairs in photosynthesis: comparison of the donor acceptor distances in photosystem I and bacterial reaction centers. Ber. Bunsenges. Phys. Chem. 100, 2041–2044.

    Article  CAS  Google Scholar 

  • Zech, S.G., Bittl, R., Gardiner, A.T. and Lubitz W., (1997a) Transient and pulsed EPR spectroscopy on the radical pair state P865+Qn to study light-induced changes in bacterial reaction centers. Appl. Magn. Reson. 13, 517–529.

    Article  CAS  Google Scholar 

  • Zech, S.G., van der Est, A.J. and Bittl, R., (1997b) Measurement of cofactor distances between P700 + and Ai in native and quinone substituted photosystem I using pulsed electron paramagnetic resonance spectroscopy. Biochem. 36, 9774–9779.

    Article  CAS  Google Scholar 

  • Zech, S.G., Kurreck, J., Eckert, H.J., Renger, G., Lubitz W. and Bittl, R. (1997c) Pulsed EPR measurement of the distance between P680+ and QA in Photosystem II. FEBS Letters 414, 454–456.

    Article  PubMed  CAS  Google Scholar 

  • Zech, S.G., Kurreck, J., Renger, G., Lubitz W. and Bittl, R. (1999) Determination of the distance between Yz X and QA in photosystem II by pulsed EPR spectroscopy on light-induced radical pairs. FEBS Letters 442, 79–82.

    Article  PubMed  CAS  Google Scholar 

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Author information

Authors and Affiliations

  1. Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, Novosibirsk, Russia

    Sergei A. Dzuba

  2. Department of Biophysics, Leiden University, Leiden, The Netherlands

    Arnold J. Hoff

Authors
  1. Sergei A. Dzuba
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  2. Arnold J. Hoff
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Editor information

Editors and Affiliations

  1. Ohio State University, Columbus, Ohio, USA

    Lawrence J. Berliner

  2. Department of Chemistry and Biochemistry, University of Denver, 80208, Denver, Colorado, USA

    Gareth R. Eaton  & Sandra S. Eaton  & 

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© 2002 Kluwer Academic / Plenum Publishers, New York

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Dzuba, S.A., Hoff, A.J. (2002). Photo-Induced Radical Pairs Investigated Using Out-Of-Phase Electron Spin Echo. In: Berliner, L.J., Eaton, G.R., Eaton, S.S. (eds) Distance Measurements in Biological Systems by EPR. Biological Magnetic Resonance, vol 19. Springer, Boston, MA. https://doi.org/10.1007/0-306-47109-4_13

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  • DOI: https://doi.org/10.1007/0-306-47109-4_13

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4757-0575-1

  • Online ISBN: 978-0-306-47109-4

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