Skip to main content
SpringerLink
Log in

Role of Charge Transfer States of the Special Pair in Primary Photosynthetic Charge Separation

  • Conference paper
Perspectives in Photosynthesis

Part of the book series: The Jerusalem Symposia on Quantum Chemistry and Biochemistry ((JSQC,volume 22))

Abstract

We propose a model for primary charge separation in the reaction centers of photosynthetic bacteria based upon an internal charge transfer state of the special pair dimer. In our model, this state serves as a trigger for primary electron transfer, linking the excited state of the special pair (with which it is nearly in resonance) to a superexchange pathway coupled to the initial bacteriopheophytin acceptor. The recombination reaction is not similarly facilitated because the charge transfer state is not close in energy to the ground state; this could be a key factor in explaining the high quantum yield of the primary electron transfer event. The model provides a qualitative explanation for three important experimental measurements (Stark effect, photochemical holeburning, singlet-triplet splitting of the charge separated species) on the reaction center. In addition, its predictions are in excellent accord with recent studies of a genetically modified reaction center in which one bacteriochlorophyll molecule of the special pair is changed to a pheophytin. For this system, one can directly observe the proposed charge transfer state participating in the electron transfer kinetics, located at an energy compatible with our model calculations.

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

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 39.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 54.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Deisenhofer, J., Epp, O., Miki, K., Huber, R. and Michel, H. (1985) ‘Structure of the protein subunits in the photosynthetic reaction center of Rhodopseudomonas viridis at 3 Å resolution’, Nature, 318, 618–624.

    Article  Google Scholar 

  2. Allen, J. P., Feher, G., Yeates, T. O., Komiya, H. and Rees, D. C. (1988) ‘Structure of the reaction center from Rhodobacter sphaeroides R-26: Protein-cofactor (quinones and Fe2+) interactions’, Proc. Natl. Acad. Sci. USA, 85, 8487–8491.

    Article  PubMed  CAS  Google Scholar 

  3. Chang, C- H., Tiede, D. M., Tang, J., Smith, U., Norris, J. R. and Schiffer, M. (1986) ‘Structure of Rhodopseudomonas sphaeroides R-26 reaction center’, FEBS Lett., 205, 82–86.

    Article  PubMed  CAS  Google Scholar 

  4. Friesner, R. A. and Won, Y. (1989) ‘Spectroscopy and electron transfer dynamics of the bacterial photosynthetic reaction center’, Biochim. Biophys. Acta, submitted.

    Google Scholar 

  5. Kirmaier, C., Holten, D., Bylina, E. J. and Youvan, D. C. (1988) ‘Electron transfer in a genetically modified bacterial reaction center containing a heterodimer’, Proc. Nad. Acad. Sci. USA, 85, 7562–7566.

    Article  CAS  Google Scholar 

  6. Kirmaier, C. and Holten, D. (1987) ‘Primary photochemistry of reaction centers from the photosynthetic bacteria’, Photosynthesis Res., 13, 225–260.

    Article  CAS  Google Scholar 

  7. Breton, J., Martin, J- L., Migus, A., Antonetti, A. and Orszag, A. (1986) ‘Femtosecond spectroscopy of excitation energy transfer and initial charge separation in the reaction center of the photosynthetic bacterium Rhodopseudomonas viridis’, Proc. Natl. Acad. Sci. USA, 83, 5121–5125.

    Article  PubMed  CAS  Google Scholar 

  8. Martin, J- L., Breton, J., Hoff, A. J., Migus, A. and Antonetti, A. (1986) ‘Femtosecond spectroscopy of electron transfer in the reaction center of photosynthetic bacterium Rhodopseudomonas sphaeroides R-26: Direct electron transfer from the dimeric bacteriochlorophyll primary donor to the bacteriopheophytin acceptor with a time constant of 2.8 ± 0.2 psec.’, Proc. Natl. Acad. Sci. USA, 83, 957–961.

    Article  PubMed  CAS  Google Scholar 

  9. Bixon, M., Jortner, J., Michel-Beyerle, M. E., Orgodnik, A. and Lersch, W. (1987) ‘The role of the accessory bacteriochlorophyll in the reaction centers of photosynthetic bacteria: Intermediate acceptor in the primary electron transfer?’ Chem. Phys. Lett., 140, 626–630.

    Article  CAS  Google Scholar 

  10. Won, Y. and Friesner, R. A. (1988) ‘Simulation of optical spectra from the reaction center of Rhodopseudomonas viridis’, J. Phys. Chem., 92, 2208–2214.

    Article  CAS  Google Scholar 

  11. Won, Y. and Friesner, R. A. (1988) ‘A thermal expansion model for the special pair of the bacterial reaction center’, Israel J. Chem, 28, 67–72.

    CAS  Google Scholar 

  12. Lockhart, D. J. and Boxer, S. G. (1988) ‘Stark effect spectroscopy of Rhodobacter sphaeroides and Rhodopseudomonas viridis reaction centers’, Proc. Natl. Acad. Sci. USA, 85, 107–111.

    Article  PubMed  CAS  Google Scholar 

  13. Lösche, M., Feher, G. and Okamura, M. Y. (1987) ‘The stark effect in reaction centers from Rhodobacter sphaeroides R-26 and Rhodopseudomonas viridis’, Proc. Natl. Acad. Sci. USA, 84, 7537–7541.

    Article  PubMed  Google Scholar 

  14. Boxer, S.G., Lockhard, D.J. and Middendorf, T.R. (1986) ‘Photochemical holeburning in photosynthetic reaction centers’, Chem. Phys. Lett., 123, 476–482.

    Article  CAS  Google Scholar 

  15. Boxer, S.G., Midendorf, T.R. and Lockhart, DJ. (1986) ‘Reversible photochemical holeburning in Rhodopseudomonas viridis reaction centers’, FEBS Lett., 200, 237–241.

    Article  CAS  Google Scholar 

  16. Meech, S.R., Hoff, A J. and Wiersma, D.A. (1985) ‘Evidence for a very early intermediate in bacterial photosynthesis. A photon-echo and hole-burning study of the primary donor band in Rhodopseudomonas sphaeroides’, Chem. Phys. Lett., 121, 287–292.

    Article  CAS  Google Scholar 

  17. Boxer, S. J., Gottfried, D. S., Lockhart, D. J. and Middendorf, T. R. (1987) ‘Nonphotochemical holeburning in a protein matrix: Chlorophyllide in apomyoglobin’, J. Chem. Phys. 86, 2439–2441.

    Article  CAS  Google Scholar 

  18. Tang, D., Jankowiak, R., Small, G. and Tiede, D. M. (1989) ‘Structured hole burned spectra of the primary donor state absorption region of Rhodopseudomonas viridi’, Chem. Phys., 131, 99–113.

    Article  CAS  Google Scholar 

  19. Hayes, J. M., Gillie, J. K., Tang, D. and Small, G. (1988) ‘Theory for spectral hole burning of the primary electron donor state of photosynthetic reaction centers’, Biochim. Biophys. Acta, 932, 287–305.

    Article  CAS  Google Scholar 

  20. Won, Y. and Friesner, R. A. (1987) ‘Simulation of photochemical hole-burning experiments on photosynthetic reaction centers’, Proc. Natl. Acad. Sci. USA, 84, 5511–5515.

    Article  PubMed  CAS  Google Scholar 

  21. Won, Y. and Friesner, R. A. (1988) ‘Theoretical studies of photochemical hole burning in photosynthetic bacterial reaction centers’, J. Phys. Chem., 92, 2214–2219.

    Article  CAS  Google Scholar 

  22. Ogrodnik, A., Lersch, W., Michel-Beyerle, M. E., Deisenhofer, J. and Michel, H. (1985) ‘Spin dipolar interaction of radical pairs in photosynthetic reaction centers’, in Michel-Beyerle, M. E. (ed.), Antennas and Reaction Centers of Photosynthetic Bacteria — Structure, Interactions, and Dynamics, Springer-Verlag, Berlin, pp. 198–206.

    Google Scholar 

  23. Marcus, R. A. (1987) ‘Superexchange versus an intermediate BChl− mechanism in reaction centers of photosynthetic bacteria’, Chem. Phys. Lett., 133, 471–477.

    Article  CAS  Google Scholar 

  24. Treutlein, H., Schulten, K., Niedermeier, C, Deisenhofer, J., Michel, H. and De Vault, D. (1988) ‘Electrostatic control of electron transfer in the photosynthetic reaction center of Rhodopseudomonas viridis’, in Breton, J. and Vermèglio, A. (eds.) Photosynthetic Bacterial Reaction Center: Structure and Dynamics, vol. 149, Plenum, New York, pp. 369–377.

    Google Scholar 

  25. Won, Y. and Friesner, R. A. (1988) ‘On the viability of the superexchange mechanism in the primary charge separation step of bacterial photosynthesis’, Biochim. Biophys. Acta, 935, 9–18.

    Article  CAS  Google Scholar 

  26. Shuvalov, V. A. and Parson, W. W. (1981) ‘Energetics and kinetics of radical pairs involving bacteriochlorophyll and bacteriopheophytin in bacterial reaction centers’, Proc. Nad. Acad. Sci. USA, 78, 957–961.

    Article  CAS  Google Scholar 

  27. Fischer, S. F. and Scherer, P. O. J. (1987) ‘On the early charge separation and recombination processes in bacterial reaction centers’, Chemical Physics, 115, 151–158.

    Article  CAS  Google Scholar 

  28. Parson, W. W., and Warshel, A. (1987) ‘The spectroscopic properties of photosynthetic reaction centers II. Application of the theory to Rhodopseudomonas viridis’, J. Am. Chem. Soc, 109, 6152–6163.

    Article  CAS  Google Scholar 

  29. Bylina, E. J. and Youvan, D. C. (1988) ‘Directed mutations affecting spectroscopic and electron transfer properties of the primary donor in the photosynthetic reaction center’, Proc. Natl. Acad. Sci. USA, 85, 7226–7230.

    Article  PubMed  CAS  Google Scholar 

  30. Breton, J., Bylina, E. J. and Youvan, D. C., this volume.

    Google Scholar 

  31. Norris, J. R., Bylina, E. J. and Youvan, D. C., this volume.

    Google Scholar 

  32. Felton, R. H. (1978) ‘Primary redox reactions of metalloporphyrins’, in Dolphin, D. (ed.), The Porphyrins, Academic Press, New York, pp. 53–125.

    Google Scholar 

  33. Kirmaier, C., Holten, D. and Sessler, J. L., personal communication.

    Google Scholar 

  34. Wasielewski, M. R., this volume.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Texas at Austin, Austin, Texas, 78712, USA

    Richard A. Friesner & Youngdo Won

Authors
  1. Richard A. Friesner
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Youngdo Won
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Department of Chemistry, University of Tel-Aviv, Israel

    J. Jortner

  2. Institut de Biologie Physico-Chimique (Fondation Edmond de Rothschild), Paris, France

    B. Pullman

Rights and permissions

Reprints and permissions

Copyright information

© 1990 Kluwer Academic Publishers

About this paper

Cite this paper

Friesner, R.A., Won, Y. (1990). Role of Charge Transfer States of the Special Pair in Primary Photosynthetic Charge Separation. In: Jortner, J., Pullman, B. (eds) Perspectives in Photosynthesis. The Jerusalem Symposia on Quantum Chemistry and Biochemistry, vol 22. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0489-7_26

Download citation

  • DOI: https://doi.org/10.1007/978-94-009-0489-7_26

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6706-5

  • Online ISBN: 978-94-009-0489-7

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation