On the Nature of the Primary Photochemical Events in Rhodopsin and Bacteriorhodopsin

  • M. Ottolenghi
  • M. Sheves
Part of the Springer Proceedings in Physics book series (SPPHY, volume 20)


All rhodopsins, whether responsible for the visual process (visual pigments-Rh), photosynthetic activity (bacteriorhodopsin-bR and halorhodopsin), phototaxis (sensory rhodopsin-sR), or photoisomerization (Retinochrome), share the same basic chromophore system: a retinyl polyene, bound to the opsin via a protonated Schiff base linkage with a lysine e- amino group [1]. Moreover, most rhodopsins (e.g., Rh, bR and sR) exhibit photocycles with remarkably similar features [1]. Primarily (see Fig. 1) The occurrence of an early red shifted photointermediate, the deprotonation of the Schiff base during subsequent stages, the photoreversibility of most intermediates, the time scales associated with various stages of the photocycle, etc. It is the purpose of this overview to discuss in a comparative way the primary photochemical steps in Rh and bR, as monitored by optical, resonance-Raman, FTIR and NMR spectroscopy. Interpretation of such phenomena in terms of the primary molecular changes occurring in the retinal moiety and its protein environment is an essential pre-requisite for understanding the mechanism by which retinoid pigments convert, store and subsequently utilize, solar radiation. Such topics will be addressed in light of recent progress and still open questions.


Primary Event Schiff Base Visual Pigment Purple Membrane Bovine Rhodopsin 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. [1]
    For reviews, see: a). W. Stoeckenius, R.H. Lozier, R.A. Bogomolni: Biochim. Biophys. Acta 505, 215 (1979); b) M. Ottolenghi: Adv. Photochem. 12, 97 (1980), c) M. Ottolenghi: in: Biomembranes, Part I, Visual Pigments and Purple Membranes, II. Methods in Enzymology, ed. by L. Packer, p. 470 (Academic Press, N.Y, 1982)CrossRefGoogle Scholar
  2. [2]
    K. Peters, M.L. Applebury, P.M. Rentzepis: Proc. Nat. Acad. Sci. USA 74, 3119 (1977).ADSCrossRefGoogle Scholar
  3. [3]
    M.L. Applebury, K.S. Peters, P.M. Rentzepis: Biophys. J. 23, 375 (1978)CrossRefGoogle Scholar
  4. [4]
    U. Dinur, B. Honig, M. Ottolenghi: in Development in Biophysical Research, ed. by A. Borsellino, P. Omodeo, R. Strom, A. Vecli, E. Wanke, pp. 209–222 (Plenum, New York, London 1980), Photochem. Photobiol. 33, 523 (1980).CrossRefGoogle Scholar
  5. [5]
    E.P. Ippen, A. Shank, A. Lewis, MA. Marcus: Science 200, 1279 (1978)ADSCrossRefGoogle Scholar
  6. [6]
    H.J. Polland, W. Zinth, W. Kaiser In Ultrafast Phenomena, ed. by D.H. Auston, K.B. Eisenthal (Springer, Berlin 1984) p. 456.Google Scholar
  7. [7]
    H.J. Polland, M.A. Franz, W. Zinth, W. Kaiser, E. Koling, D. Oesterhelt: Biophys. J. 49, 651 (1986).CrossRefGoogle Scholar
  8. [8]
    M.C. Nuss, W. Zinth, W. Kaiser, E. Koling and D. Oesterhelt: Chem. Phys. Lett. 117, 1 (1986).ADSCrossRefGoogle Scholar
  9. [9]
    M.C. Downer, M. Islam, C.V. Shank, A. Harootunian, A. Lewis: In Ultrafast Phenomena, ed. by D.H. Auston, K.B. Eisenthal (Springer, Berlin 1984) p. 500.Google Scholar
  10. [10]
    A.V. Sharkov, A.V. Pakulev, Y.A. Martreetz: Biochim. Biophys. Acta 808, 94 (1985).CrossRefGoogle Scholar
  11. [11]
    J.L. Martin, J.W. Petrich, J. Breton, A. Orszag: This volume.Google Scholar
  12. [12]
    B. Becher and T.G. Ebrey: Biochem. Biophys. Res. Commun. 69, 1 (1976).CrossRefGoogle Scholar
  13. [13]
    M.A. El Sayed, B. Karvali and J. Fukumoto: Proc. Natl. Acad. Sci. USA 78, 7512 (1981).ADSCrossRefGoogle Scholar
  14. [14]
    Y. Schichida, S. Matuoka, T. Yoshizawa: Photochem. Photobiophys. 7, 221 (1984); T. Yoshizawa, Y. Shichida, S. Matuoka: Vision Res. 24, 1455 (1984).Google Scholar
  15. [15]
    T. Yoshizawa, S. Horiuchi: In Biochemistry and Physiology of Visual Pigments, ed. by H. Langer (Springer-Verlag, Berlin 1973) p. 69.CrossRefGoogle Scholar
  16. [16]
    N. Sasaki, F. Tokunaga, T. Ogurusu, T. Yoshizawa: Photochem. Photobiophys. 7, 341 (1984).Google Scholar
  17. [17]
    T. Kobayashi: Photochem. Photobiol. 32, 207 (1980); T. Kobayashi, S. Nagakura: In Methods in Enzymology, Vol. 81 f1 (Academic Press, N.Y, 1982) p. 51.CrossRefGoogle Scholar
  18. [18]
    T. Rosenfeld, B. Honig, M. Ottolenghi, J. Hurley, T.G. Ebrey: Pure Appl. Chem. 49 341 (1977); J. Hurley, T.G. Ebrey, B. Honig, M. Ottolenghi: Nature (London) 540 (1977).CrossRefGoogle Scholar
  19. [19]
    B. Aton, R. Callender, B. Honig: Nature (London) 273, 784 (1978).ADSCrossRefGoogle Scholar
  20. [20]
    S. Kawamura, S. Miyatani, H. Matsumoto, T. Yoshizawa, R.S.H. Liu: Biochemistry 19, 1549 (1980).CrossRefGoogle Scholar
  21. [21]
    G. Erying, B. Curry, A. Broek, J. Lugtenburg, R. Mathies: Biochemistry 21, 384 (1982).CrossRefGoogle Scholar
  22. [22]
    M. Braiman and R. Mathies: Proc. Natl. Acad. Sci. USA 79, 403 (1983).ADSCrossRefGoogle Scholar
  23. [23]
    H. Akita, S.P. Tanis, M. Adams, V. Balogh-Nair, K. Nakanishi: J. Am. Chem. Soc. 102, 6370 (1980); B. Mao, M. Tsuda, T.G. Ebrey, H. Akita, V. Balogh-Nair, K. Nakanishi: Biophys. J. 35, 543 (1981); T. Yoshizawa, Y. Shichida, S. Matuoka, N. Sasaki, K. Nakanishi, V. Balogh-Nair, H. Akita: Zool. Mag. 92 535,1983.CrossRefGoogle Scholar
  24. [24]
    J.O. Fang, J. Carriker, V. Balogh-Nair, K. Nakanishi: J. Am. Chem. Soc. 105, 5162 (1983); C.H. Chang, R. Govindjee, T. Ebrey, K.A. Bagley, G. Dollinger, L. Eisenstein, J. Marque, H. Roder, J. Vittitow, J.O. Fang, K. Nakanishi: Biophys. J. 47, 509 (1985).CrossRefGoogle Scholar
  25. [25]
    M. Sheves, N. Friedman, A. Albeck, M. Ottolenghi: Biochemistry 24, 1260 (1985).CrossRefGoogle Scholar
  26. [26]
    A. Albeck, N. Friedman, M. Sheves, M. Ottolenghi: J. Am. Chem. Soc. 108, 4614 (1986).CrossRefGoogle Scholar
  27. [27]
    G.S. Harbison, S.O. Smith, J.A. Pardoen, C. Winkel, J. Lugtenburg, J. Harzfeld, R. Mathies, R.G Griffin: Proc. Natl. Acad. Sci, USA 81, 1706 (1984).ADSCrossRefGoogle Scholar
  28. [28]
    S.O. Smith, A.B. Myers, J.A. Pardoen, C. Winkel, P.PJ. Mulder, J. Lugtenburg, R. Mathies: Proc. Natl. Acad. Sci. USA 81, 2055 (1984).ADSCrossRefGoogle Scholar
  29. [29]
    A. Warshel: Proc. Natl. Acad. USA 75, 25587 (1978).Google Scholar
  30. [30]
    K. Schulten, P. Tavan: Nature (London), 272, 85 (1978); P. Tavan, K. Schulten: Biophys. J, 50, 81 (1986).ADSCrossRefGoogle Scholar
  31. [31]
    R.S.H. Liu, D. Mead, A.E. Asato: J. Am. Chem. Soc. 107, 6609 (1985).CrossRefGoogle Scholar
  32. [32]
    R.S.H. Liu, A.E. Asato: Proc. Natl. Acad. Sci. USA 82, 259 (1985).ADSCrossRefGoogle Scholar
  33. [33]
    S.O. Smith, AM. Myers, J.A. Pardoen, C. Winkel, P.P.J. Mulder J. Lugtenburg, R. Mathies: Proc. Natl. Acad. USA 81, 2055 (1984); S.O. Smith, J. Lugtenburg, R. Mathies: J. Membr. Biol. 85, 109 (1985).ADSCrossRefGoogle Scholar
  34. [34]
    K. Gerwert and F. Siebert: The EMBO J. 5, 805 (1986).Google Scholar
  35. [35]
    A.V. Sharkov, YuA. Matveetz, S.V. Chekalin, A.V. Konyashchenko, O.M. Brekhov, B.Yu. Rootskov: Photochem. Photobiol. 38, 108 (1983).CrossRefGoogle Scholar
  36. [36]
    R.R. Alfano, W.Y.R. Govindjee, B. Becher, T.G. Ebrey: Biophys. J. 16, 541 (1976).CrossRefGoogle Scholar
  37. [37]
    S.L. Shapiro, A.J. Campillo, A. Lewis, J. Perrault, J.P. Spoonhower, R.K. Klayton, W. Stoeckenius: Biophys. J. 23, 383 (1978).CrossRefGoogle Scholar
  38. [38]
    T. Kouyama, K. Kinosita, A. Ikegami: Biophys. J. 47, 43 (1985).CrossRefGoogle Scholar
  39. [39]
    R.R. Birge: Ann. Rev. Biophys. Bioeng. 10, 315 (1981).CrossRefGoogle Scholar
  40. [40]
    T. Gillbro, V. Sundstrom: Photochem. Photobiol. 37, 455 (1983).CrossRefGoogle Scholar
  41. [41]
    B. Honig, T. Ebrey, R.H. Callendar, U. Dinur, M. Ottolenghi: Proc. Natl. Acad. Sci. USA 76, 2503 (1979).ADSCrossRefGoogle Scholar
  42. [42]
    A. Cooper: Nature (London) 282, 531 (1979).ADSCrossRefGoogle Scholar
  43. [43]
    F. Boucher, R.M. Le Blanc: Photochem. Photobiol. 41, 459 (1985).CrossRefGoogle Scholar
  44. [44]
    R.R. Birge, T.H. Cooper: Biophys. J. 42, 61 (1983).CrossRefGoogle Scholar
  45. [45]
    R.R. Birge, L.M. Hubbard: J. Am. Chem. Soc. 102, 2195 (1980); R.R. Birge, L.M. Hubbard: Biophys. J. 34, 517 (1981).CrossRefGoogle Scholar
  46. [46]
    A. Warshel and N. Barboy: J. Am. Chem. Soc. 104, 1469 (1982).CrossRefGoogle Scholar
  47. [47]
    M. Sheves, T. Baasov, N. Friedman, M. Ottolenghi, R. Feinmann-Weinberg, V. Rosenbach, B. Ehrenberg: J. Am. Chem. Soc. 106, 2435 (1984).CrossRefGoogle Scholar
  48. [48]
    J. Terner, C.L. Hsieh, A.R. Burns, M.A. El-Sayed: Proc. Natl. Acad. Sci. USA 76, 3046 (1979); J. Terner, A.M. El-Sayed, Acc. Chem. Res. 18, 331 (1985).ADSCrossRefGoogle Scholar
  49. [49]
    A.B. Meyers, R.A. Harris, R.A. Mathies: J. Chem. Phys. 79, 603; D. Stern and R. Mathies: In: Time-Resolved Vibrational Spectroscopy, ed. by M. Stockburger, A. Laubreau, Vol. 4, 250 (Springer-Verlag Proceedings in Physics (1985).ADSCrossRefGoogle Scholar
  50. [50]
    K.J. Rothschild, H. Marrero, M. Braiman, R. Mathies,: Photochem. Photobiol. 40, 675 (1984).CrossRefGoogle Scholar
  51. [51]
    K.J. Rothschild, H. Marrero: Proc. Natl. Acad. Sci. USA 79, 4045 (1982); K.J. Rothschild, P. Roepe, J. Lugtenburg, J.A. Pardoen: Biochemistry 23, 6103 (1984).ADSCrossRefGoogle Scholar
  52. [52]
    K. Bagley, G. Dollinger, L. Eisenstein, A.K. Singh, L. Zimenyi: Proc. Natl. Acad. USA 79, 4972 (1982).ADSCrossRefGoogle Scholar
  53. [53]
    G. Eyring, R.A. Mathies: Proc. Natl. Acad. Sci. USA 76, 33 (1979).ADSCrossRefGoogle Scholar
  54. [54]
    B. Aton, A.G. Doukas, D. Narva, R.H. Callender, U. Dinur, B. Honig: Biophys. J. 29, 79 (1980); D. Narva, RH. Callender; Photochem. Photobiol. 32, 273 (1980).CrossRefGoogle Scholar
  55. [55]
    I. Palings, J.A. Pardoen, E. Van den Berg, G. Winkel, J. Lugtenburg, R. Mathies: Biochemistry, in press (1987).Google Scholar
  56. [56]
    K.A. Bagley, V. Balogh-Nair, A.A. Croteau, G. Dollinger, T.G. Ebrey, M. Hong, K. Nakanishi, J. Vittitow: Biochemistry 24, 6055 (1985).CrossRefGoogle Scholar
  57. [57]
    M. Sheves, T. Baasov, N. Friedman: Biochemistry, in press (1987).Google Scholar
  58. [58]
    K. Rothschild, P. Roeppe, P.L. Ahl, T.N. Earnest, RA. Bogomolni, S.A. Das Gupta, GM. Mulliken, J. Herzfeld: Proc. Natl. Acad. Sci. USA 83, 347 (1986).ADSCrossRefGoogle Scholar
  59. [59]
    G. Dollinger, L. Eisenstein, S.-L. Lin, K. Nakanishi, J. Termini: Biochemistry 25, 6524 (1986).CrossRefGoogle Scholar
  60. [60]
    T. Kobayashi, K. Ogasawara, S. Koshihara, K. Ichimura, R. Hara: This volume.Google Scholar
  61. [61]
    T. Hara, R. Hara: Methods in Enzymology 81, 190 (1982).CrossRefGoogle Scholar
  62. [62]
    G. Harbison, J. Herzfeld, R Griffin: Biochemistry 22, 1 (1983).CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1987

Authors and Affiliations

  • M. Ottolenghi
    • 1
  • M. Sheves
    • 2
  1. 1.Department of Physical ChemistryThe Hebrew University of JerusalemJerusalemIsrael
  2. 2.Department of Organic ChemistryThe Weizmann Institute of ScienceRehovotIsrael

Personalised recommendations