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Spectroscopic studies of carotenoids in photosynthetic systems

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Book cover Carotenoids in Photosynthesis

Abstract

This chapter is designed to be complementary to Chapter 8. It is intended to be an introduction to a few very powerful but still developing spectroscopic techniques, i.e. electronic, Raman and magnetic resonance spectroscopies, for biologists, chemists and physicists who are interested in “carotenoids in photosynthesis”. It is not a comprehensive catalogue of the results of spectroscopic techniques. The main emphasis of this chapter is on spectroscopic studies of structures and excited-state properties of carotenoids both free in solution and bound to the reaction centre (RC) or the light-harvesting complex (LHC) of phototrophic bacteria; ß-carotene, however, is also discussed as a prototype or model carotenoid. Each section of this chapter is divided into two parts: the first is written for a newcomer to the particular field of spectroscopy, is entitled “Fundamentals”, and provides the reader with a brief description of spectroscopic background that is brief but sufficient for one to understand and appreciate the results obtained when the technique is applied. The second part, which is entitled “Examples of Application”, is intended to serve as a handbook or a manual for a carotenoid spectroscopist and consists of a list of classical and up-to-date examples. Here, fundamental data which may be necessary or useful for day-to-day research work are included; some unpublished data which are expected to be important in the future are also given. Because of shortage of space all the experimental details have not been described; the original papers should be consulted. The results from different spectroscopic methods have not been correlated in this chapter. Such correlations form the basis of Chapter 8, and can also be found in recent reviews by Frank et al. (1991), Koyama (1991) and Mimuro and Katoh (1991).

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References

  • Andersson, P.O., Gillbro, T., Ferguson, L. and Cogdell, R.J. (1990) Spectral shift of purple bacterial carotenoids related to solvent and protein polarizability. In: Baltscheffsky, M. (ed.), Current Research in Photosynthesis ,Vol. II, Kluwer Academic Publishers, Dordrecht, pp. 117–120.

    Google Scholar 

  • Andersson, P.O., Gillbro, T., Ferguson, L. and Cogdell, R. J. (1991) Absorption spectral shifts of carotenoids related to medium polarizability. Photochem. Photobiol. ,54:353–360.

    Article  CAS  Google Scholar 

  • Basu, S. (1964) Theory of solvent effects on molecular electronic spectra. Adv. QuantumChem. ,1:145–169.

    Article  CAS  Google Scholar 

  • Bensasson, R., Land, E.J. and Maudinas, B. (1976) Triplet states of carotenoids from photosynthetic bacteria studied by nanosecond ultraviolet and electron pulse irradiation. Photochem. Photobiol. ,23:189–193.

    Article  PubMed  CAS  Google Scholar 

  • Boucher, F., Rest, M. van der and Gingras, G. (1977) Structure and function of carotenoids in the photoreaction center from Rhodospirillum rubrum. Biochim. Biophys. Acta, 461:339–357.

    Article  PubMed  CAS  Google Scholar 

  • Chadwick, B.W. and Frank, H.A. (1986) Electron-spin resonance studies of carotenoids incorporated into reaction centers of Rhodobacter sphaeroides R-26.J. Biochim. Biophys.Acta ,851:257–266.

    Article  CAS  Google Scholar 

  • Cogdell, R.J., Monger, T.G. and Parson, W.W. (1975) Carotenoid triplet states in reaction centers from Rhodopseudomonas sphaeroides and Rhodo spirillum rubrum. Biochim. Biophys. Acta ,408:189–199.

    Article  PubMed  CAS  Google Scholar 

  • Cogdell, R.J., Parson, W.W. and Kerr, M.A. (1976) The type, amount, location, and energy transfer properties of the carotenoid in reaction centers from Rhodopseudomonas sphaeroides. Biochim. Biophys. Acta ,430:83–93.

    Article  PubMed  CAS  Google Scholar 

  • Cosgrove, S. A., Guite, M.A., Burnell, T.B. and Christensen, R.L. (1990) Electronic relaxation in long polyenes. J. Phys. Chem. ,94:8118–8124.

    Article  CAS  Google Scholar 

  • Dallinger, R.F., Guanci, Jr., J.J., Woodruff, W.H. and Rodgers, M.A.J. (1979) Vibrational spectroscopy of the electronically excited state: pulse radiolysis/time-resolved resonance Raman study of triplet ß-carotene. J. Am. Chem. Soc ,101:1355–1357.

    Article  CAS  Google Scholar 

  • De Coster, B., Christensen, R.L., Gebhard, R. et al. (1992) Low-lying electronic states of carotenoids. Biochim. Biophys. Acta ,1102:107–114.

    Article  Google Scholar 

  • Englert, G. (1982) N.M.R. of carotenoids. In: Britton, G. and Goodwin, T.W. (eds.), Carotenoid Chemistry and Biochemistry. Pergamon , Oxford, pp. 107–134.

    Google Scholar 

  • Englert, G. (1985) NMR of carotenoids: New experimental techniques. Pure Appl. Chem., 57:801–821.

    Article  CAS  Google Scholar 

  • Englert, G. (1991) NMR of carotenoids: Novel experimental techniques. Pure Appl. Chem., 63:59–70.

    Article  CAS  Google Scholar 

  • Frank, H.A. (1992) Electron paramagnetic resonance studies of carotenoids. Meth. Enzymol., 213:305–312.

    Article  PubMed  CAS  Google Scholar 

  • Frank, H.A., Bolt, J.D., B. de Costa, S.M. and Sauer, K. (1980) Electron paramagnetic resonance detection of carotenoid triplet states. J. Am. Chem. Soc. ,102:4893–4898.

    Article  CAS  Google Scholar 

  • Frank, H.A., Chadwick, B.W., Taremi, S., etal. (1986) Singlet and triplet absorption spectra of carotenoids bound in the reaction centers of Rhodopseudomonas sphaeroides R-26. FEBSLett. ,203:157–163.

    Article  CAS  Google Scholar 

  • Frank, H.A., Chadwick, B.W., Oh, J.J. et al. (1987) Triplet-triplet energy transfer in B800–850 light-harvesting complexes of photosynthetic bacteria and synthetic carotenoporphyrin molecules investigated by electron spin resonance. Biochim. Biophys. Acta ,892:253– 263.

    Article  CAS  Google Scholar 

  • Frank, H.A., Violette, C.A., Trautman, J.K. et al. (1991) Carotenoids in photosynthesis: structure and photochemistry. Pure Appl. Chem. ,63:109–114.

    Article  CAS  Google Scholar 

  • Gebhard, R., van der Hoef, K., Violette, C.A. et al. (1991) 13C Magic angle spinning NMR evidence for a 15,15 ’-Z configuration of the spheroidene chromophore in the Rhodobactersphaeroides reaction center: synthesis of 13C-and 2H-labeled spheroidenes. Pure Appl.Chem. ,63: 115–122.

    Article  CAS  Google Scholar 

  • Gottfried, D.S., Steffen, M.A. and Boxer, S.G. (1991a) Large protein-induced dipoles for a symmetric carotenoid in a photosynthetic antenna complex. Science ,251: 662–665.

    Article  PubMed  CAS  Google Scholar 

  • Gottfried, D.S., Steffen, M.A. and Boxer, S.G. (1991b) Stark effect spectroscopy of carotenoids in photosynthetic antenna and reaction center complexes. Biochim. Biophys.Acta ,1059: 76–90.

    Article  PubMed  CAS  Google Scholar 

  • Hashimoto, H. and Koyama, Y. (1988) Time-resolved resonance Raman spectroscopy of triplet ß-carotene produced from all-trans, 7-cis, 9-cis, 13-cis ,and 15-cis isomers and high-pressure liquid chromatography analyses of photoisomerisation via the triplet state. J. Phys. Chem. ,92: 2101–2108.

    Article  CAS  Google Scholar 

  • Hashimoto, H. and Koyama, Y. (1989a) The C=C stretching Raman lines of ß-carotene isomers in the S1 state as detected by pump-probe resonance Raman spectroscopy. Chem.Phys. Lett. ,154: 321–325.

    Article  CAS  Google Scholar 

  • Hashimoto, H. and Koyama, Y. (1989b) Raman spectra of all-frans-ß-carotene in the S1 and T states produced by direct photoexcitation. Chem. Phys. Lett. ,163: 251–256.

    Article  CAS  Google Scholar 

  • Hashimoto, H., Koyama, Y., Ichimura, K. and Kobayashi, T. (1989) Time-re solved absorption spectroscopy of the triplet state produced from the all-trans, 1-cis, 9-cis, 13-cis ,and 15-cis isomers of ß-carotene. Chem. Phys. Lett. ,162: 517–522.

    Article  CAS  Google Scholar 

  • Hashimoto, H., Koyama, Y., Hirata, Y. and Mataga, N. (1991) S1 and T1 species of ß-carotene generated by direct photoexcitation from the all-trans, 9-cis, 13-cis ,and 15-cis isomers as revealed by picosecond transient absorption and transient Raman spectroscopies. J.Phys. Chem. ,95: 3072–3076.

    Article  CAS  Google Scholar 

  • Hayashi, H., Noguchi, T. and Tasumi, M. (1989) Studies on the interrelationship among the intensity of a Raman marker band of carotenoids, polyene chain structure, and efficiency of the energy transfer from carotenoids to bacteriochlorophyll in photosynthetic bacteria. Photochem. Photobiol ,49: 337–343.

    Article  CAS  Google Scholar 

  • Hoff, A.J. (1982) ODMR spectroscopy in photosynthesis II: the reaction center triplet in bacterial photosynthesis. In: Clarke, R.J.H. (ed.), Triplet State ODMR Spectroscopy:Techniques and Applications to Biophysical Systems ,A Wiley-Interscience Publication, New York, pp. 367–425.

    Google Scholar 

  • Inagaki, F., Tasumi, M. and Miyazawa, T. (1974) Excitation profile of the resonance Raman effect of ß-carotene. J. Mol. Spectrosc ,50: 286–303.

    Article  CAS  Google Scholar 

  • Kohler, B.E., Spangler, C. and Westerfield, C. (1988) The 2’A state in the linear polyene 2,4,6,8,10,12,14,16-octadecaoctaene. J. Chem. Phys. ,89: 5422–5428.

    Article  CAS  Google Scholar 

  • Koyama, Y. (1991) Structures and functions of carotenoids in photosynthetic systems. J.Photochem. Photobiol. B: Biol. ,9: 265–280.

    Article  CAS  Google Scholar 

  • Koyama, Y., Long, R.A., Martin, W.G. and Carey, P.R. (1979) The resonance Raman spectrum of carotenoids as an intrinsic probe for membrane potential: oscillatory changes in the spectrum of neurosporene in the chromatophores of Rhodopseudomonassphaeroides. Biochim. Biophys. Acta ,548: 153–160.

    Article  PubMed  CAS  Google Scholar 

  • Koyama, Y., Kito, M., Takii, T. et al. (1982) Configuration of the carotenoid in the reaction centers of photosynthetic bacteria: comparison of the resonance Raman spectrum of the reaction center of Rhodopseudomonas sphaeroides G1C with those of cis-trans isomers of ß-carotene. Biochim. Biophys. Acta ,680: 109–118.

    Article  CAS  Google Scholar 

  • Koyama, Y., Tahara, M. and Segawa, S. (1983 a) A slow phase of the carotenoid shift induced by pH jump or by continuous illumination: an electron absorption and resonance Raman study on chromatophores of Rhodopseudomonas sphaeroides G1C. Photobiochem.Photobiophys. ,6: 329–338.

    CAS  Google Scholar 

  • Koyama, Y., Takii, T., Saiki, K. and Tsukida, K. (1983b) Configuration of the carotenoid in the reaction centers of photosynthetic bacteria (2): comparison of the resonance Raman lines of the reaction centers with those of the 14 different cis-trans isomers of ß-carotene. Photobiochem. Photobiophys. ,5: 139–150.

    CAS  Google Scholar 

  • Koyama, Y., Kanaji, M. and Shimamura, T. (1988a) Configurations of neurosporene isomers isolated from the reaction center and the light-harvesting complex of Rhodobactersphaeroides G1C: a resonance Raman, electronic absorption, and 1H NMR study. Photochem. Photobiol. ,48: 107–114.

    Article  CAS  Google Scholar 

  • Koyama, Y., Takatsuka, I., Nakata, M. and Tasumi, M. (1988b) Raman and infrared spectra of the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers of ß-carotene: key bands distinguishing stretched or terminal-bent configurations from central-bent configurations. J. Raman Spectrosc ,19: 37–49.

    Article  CAS  Google Scholar 

  • Koyama, Y., Hosomi, M., Hashimoto, H. and Shimamura, T. (1989) 1H NMR spectra of the all-trans, 1-cis, 9-cis, 13-cis and 15-cis isomers of ß-carotene: elongation of the double bond and shortening of the single bond toward the center of the conjugated chain as revealed by vicinal coupling constants. J. Mol. Struct. ,193: 185–201.

    Article  CAS  Google Scholar 

  • Koyama, Y., Takatsuka, I., Kanaji, M. et al. (1990) Configurations of carotenoids in the reaction center and the light-harvesting complex of Rhodospirillum rubrum : natural selection of carotenoid configurations by pigment protein complexes. Photochem.PhotobioL ,51: 119–128.

    Article  CAS  Google Scholar 

  • Kuki, M., Hashimoto, H. and Koyama, Y. (1990) The 21A state of a carotenoid bound to the chromatophore membrane of Rhodobacter sphaeroides 2.4.1 as revealed by transient resonance Raman spectroscopy. Chem. Phys. Lett. ,165: 417–422.

    Article  CAS  Google Scholar 

  • Kuki, M., Koyama, Y. and Nagae, H. (1991) Triplet-sensitized and thermal isomerisation of all-trans, 1-cis, 9-cis ,13-mand 15-cis isomers of ß-carotene: configurational dependence of the quantum yield of isomerisation via the T1 state. J. Phys. Chem. ,95:7171–7180.

    Article  CAS  Google Scholar 

  • Lutz, M., Chinsky, L. and Turpin, P.Y. (1982) Triplet states of carotenoids bound to reaction centers of photosynthetic bacteria: time-resolved resonance Raman spectroscopy. Photochem. PhotobioL ,36: 503–515.

    Article  CAS  Google Scholar 

  • Mathis, P. and Kleo, J. (1973) The triplet state of ß-carotene and of analog polyenes of different length. Photochem. Photobiol. ,18: 343–346.

    Article  CAS  Google Scholar 

  • Mimuro, M. and Katoh, T. (1991) Carotenoids in photosynthesis: absorption, transfer and dissipation of light energy. Pure Appl. Chem. ,63: 123–130.

    Article  CAS  Google Scholar 

  • Mimuro, M., Nagashima, U., Takaichi, S. et al. (1992) Molecular structure and optical properties of carotenoids for in vivo energy transfer function in the algal photosynthetic pigment system. Biochim. Biophys. Acta ,1098:271–274.

    Article  CAS  Google Scholar 

  • Monger, T.G., Cogdell, R.J. and Parson, W.W. (1976) Triplet states of bacteriochlorophyll and carotenoids in chromatophores of photosynthetic bacteria. Biochim. Biophys. Acta, 449: 136–153.

    Article  PubMed  CAS  Google Scholar 

  • Naruse, M., Hashimoto, H., Kuki, M. and Koyama, Y. (1991) Triplet excitation of precursors of spirilloxanthin bound to the chromatophores of Rhodo spirillum rubrum as detected by transient Raman spectroscopy. J. Mol. Struct. ,242: 15–26.

    Article  CAS  Google Scholar 

  • Negri, F., Orlandi, G., Zerbetto, F. and Zgierski, M.Z. (1989) Theoretical study of the force field of the lowest singlet electronic states of long polyenes. J. Chem. Phys. ,91: 6215– 6224.

    Article  CAS  Google Scholar 

  • Noguchi, T., Kolaczkowski, S., Arbour, C. et al. (1989) Resonance Raman spectrum of the excited 21Ag state of ß-carotene. Photochem. PhotobioL ,50: 603–609.

    Article  CAS  Google Scholar 

  • Noguchi, T., Hayashi, H. and Tasumi, M. (1990a) Factors controlling the efficiency of energy transfer from carotenoids to bacteriochlorophyll in purple photosynthetic bacteria. Biochim. Biophys. Acta ,1017: 280–290.

    Article  CAS  Google Scholar 

  • Noguchi, T., Hayashi, H., Tasumi, M. and Atkinson, G.H. (1990b) Frequencies of the Franck-Condon active a C=C stretching mode in the 21A g exited state of carotenoids. Chem. Phys. Lett ,175: 63–169.

    Article  Google Scholar 

  • Noguchi, T., Hayashi, H., Tasumi, M. and Atkinson, G.H. (1991) Solvent effects on the a C=C stretching mode in the 21A g excited state of ß-carotene and two derivatives: picosecond time-resolved resonance Raman spectroscopy. J. Phys. Chem. ,95: 3167– 3172.

    Article  CAS  Google Scholar 

  • Shreve, A.P., Trautman, J.K., Frank, H.A. et al. (1991) Femtosecond energy-transfer processes in theB800-850light-harvesting complex of Rhodobactersphaeroides 2A.I.Biochim. Biophys. Acta ,1058: 280–288.

    Article  CAS  Google Scholar 

  • Shreve, A.P., Trautman, J.K., Owens, T.G. and Albrecht, A.C. (1991) Determination of the S2 lifetime of ß-carotene. Chem. Phys. Lett ,178: 89–96.

    Article  CAS  Google Scholar 

  • Shulten, K., Dinur, U. and Honig, B.J. (1980) The spectra of carbonium ions, cyanine dyes, and protonated Schiff base polyenes. J. Chem. Phys. ,73: 3927–3935.

    Article  Google Scholar 

  • Simpson, J.H., McLaughlin, L., Scott-Smith, D. and Christensen, R.L. (1987) Vibronic coupling in polyenes: high resolution optical spectroscopy of all-trans-2,4,6,8,10,12,14-hexadecaheptaene. J. Chem. Phys. ,87: 3360–3365.

    Article  CAS  Google Scholar 

  • Tang, J. and Albrecht, A.C. (1970) Developments in the theories of vibrational Raman intensities. In: Szymanski, H.A. (ed.), Raman Spectroscopy: Theory and Practice ,Vol. 2. Plenum Press, New York, pp. 33–68.

    Google Scholar 

  • Thrash, R.J., Fang, H.L.B. and Leroi, G.E. (1977) The Raman excitation profile spectrum of ß-carotene in the preresonance region: evidence for a low-lying singlet state. J. Chem.Phys. ,67: 5930–5933.

    Article  CAS  Google Scholar 

  • Truscott, T.G., Land, E.J. and Sykes, A. (1973) The in vitro photochemistry of biological molecules El: absorption spectra, lifetimes and rates of oxygen quenching of the triplet states of ß-carotene, retinal and related polyenes. Photochem. Photobiol. ,17: 43–51.

    Article  PubMed  CAS  Google Scholar 

  • Tsukida, K., Saiki, K., Takii, T. and Koyama, Y. (1982) Separation and determination oîcis/ trans-ß-carotenes by high-performance liquid chromatography. J. Chromatogr. ,245: 359–364.

    Article  CAS  Google Scholar 

  • Wasielewski, M.R., Tiede, D.M. and Frank, H.A. (1986) Ultrafast electron and energy transfer in reaction center and antenna proteins from photosynthetic bacteria. In: Fleming, G.R. and Siegman, A.E. (eds.), Ultrafast Phenomena V. Springer, Berlin (Springer Series in Chemical Physics 46) pp. 388–392.

    Google Scholar 

  • Wasielewski, M.R., Johnson, D.G., Bradford, E.G. and Kispert, L.D. (1989) Temperature dependence of the lowest excited singlet-state lifetime of all-trans-ß-carotene and fully deuterated all-trans-ß-carotene. J. Chem. Phys. ,91: 6691–6697.

    Article  CAS  Google Scholar 

  • Wernly, J. and Lauterwein, J. (1985) Two-dimensional NMR studies of polyene systems. Mag. Res. Chem. ,23: 170–176.

    Article  CAS  Google Scholar 

  • Wraight, C.A., Cogdell, R.J. and Chance, B. (1978) Ion transport and electrochemical gradients in photosynthetic bacteria. In: Clayton, R.K. and Sistrom, W.R. (eds.), The Photosynthetic Bacteria. Plenum, New York, pp. 471–511.

    Google Scholar 

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Authors
  1. Y. Koyama
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  2. H. Hashimoto
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Editors and Affiliations

  1. School of Biological and Earth Sciences, Liverpool John Moores University, Liverpool, L3 3AF, UK

    Andrew J. Young

  2. Department of Biochemistry, University of Liverpool, PO Box 147, Liverpool, L69 3BX, UK

    George Britton

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Koyama, Y., Hashimoto, H. (1993). Spectroscopic studies of carotenoids in photosynthetic systems. In: Young, A.J., Britton, G. (eds) Carotenoids in Photosynthesis. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2124-8_9

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  • DOI: https://doi.org/10.1007/978-94-011-2124-8_9

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