Photosynthesis Research

, Volume 83, Issue 1, pp 45–52

Resonance Raman spectroscopy of carotenoids in Photosystem II core complexes

  • Cara A. Tracewell
  • Agnes Cua
  • David F. Bocian
  • Gary W. Brudvig
Regular paper


Resonance Raman (RR) spectroscopy has been used to examine the configuration of the carotenoids bound to Synechocystis PCC 6803 Photosystem II (PS II) core complexes. The excitation wavelengths used (514.5, 488.0, 476.5 and 457.9 nm) span the absorption bands of all of the ~12–17 neutral carotenoids in the PS II core complex. The RR spectra of the two carotenoids associated with the D1–D2 polypeptides (Car507 and Car489) of the reaction center are extracted via light versus dark difference experiments measured at 20 K. The RR results are consistent with all-trans configurations for both Car507 and Car489 and indicate that majority of the other carotenoids in the PS II core complex must also be in the all-trans configuration. The configuration of β-carotene is relevant to its proposed function as a molecular wire in the secondary electron-transfer reactions of PS II.


β -carotene photosystem II resonance Raman secondary electron transfer pathway 


Car507 and Car489

carotenoids associated with the D1–D2 polypeptides of the reaction center




chlorophyll-binding protein of molecular weight 43 kDa


chlorophyll-binding protein of molecular weight 47 kDa




β-dodecyl maltoside


high pressure liquid chromatography


2-(N-morpholino)ethanesulphonic acid


Photosystem II


reaction center


resonance Raman


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Bialek-Bylka, GE, Tomo, T, Satoh, K, Koyama, Y 199515-cis-beta-carotene found in the reaction center of spinach Photosystem IIFEBS Lett363137140CrossRefPubMedGoogle Scholar
  2. Debus, RJ 2000The polypeptides of Photosystem II and their influence on manganotyrosyl-based oxygen evolutionMetal Ions Biol Syst37657711Google Scholar
  3. Ferreira, KN, Iverson, TM, Maghlaoui, K, Barber, J, Iwata, S 2004Architecture of the photosynthetic oxygen-evolving centerScience30318311838PubMedGoogle Scholar
  4. Fujiwara, M, Hayashi, H, Tasumi, M, Kanaji, M, Koyama, Y, Satoh, K 1987Structural studies on a Photosystem-II reaction-center complex consisting of D1 and D2 polypeptides and cytochrome b559 by resonance Raman spectroscopy and high performance liquid chromatographyChem Lett1020052008Google Scholar
  5. Germano, M, Pascal, A, Shkuropatov, AY, Robert, B, Hoff, AJ, Gorkom, HJ 2002Pheophytin–protein interactions in Photosystem II studied by resonance Raman spectroscopy of modified reaction centersBiochemistry411144911455CrossRefPubMedGoogle Scholar
  6. Ghanotakis, DF, Depaula, JC, Demetriou, DM, Bowlby, NR, Petersen, J, Babcock, GT, Yocum, CF 1989Isolation and characterization of the 47 KDa protein and the D1–D2–cytochrome-b-559 complexBiochim Biophys Acta9744453PubMedGoogle Scholar
  7. Hanley, J, Deligiannakis, Y, Pascal, A, Faller, P, Rutherford, AW 1999Carotenoid oxidation in Photosystem IIBiochemistry3881898195CrossRefPubMedGoogle Scholar
  8. Jeevarajan, AS, Wei, CC, Kispert, LD 1994Geometrical isomerization of carotenoids in dichloromethaneJ Chem Soc Perk T24861869CrossRefGoogle Scholar
  9. Jordan, P, Fromme, P, Witt, HT, Klukas, O, Saenger, W, Krauss, N 2001Three-dimensional structure of cyanobacterial Photosystem I at 2.5 angstrom resolutionNature411909917PubMedGoogle Scholar
  10. Kamiya, N, Shen, JR 2003Crystal structure of oxygen-evolving Photosystem II from Thermosynechococcus vulcanus at 3.7-A resolutionProc Natl Acad Sci, USA10098103Google Scholar
  11. Kohler, BE 1993Octatetraene PhotoisomerizationChem Rev934154CrossRefGoogle Scholar
  12. Koyama, Y, Fujii, R 1999

    Cis-trans carotenoids in photosynthesis: configurations, excited-state properties and physiological functions

    Frank, HAYoung, AJBritton, GCogdell, RJ eds. The Photochemistry of CarotenoidsKluwer Academic PublishersDordrecht, The Netherlands161188
    Google Scholar
  13. Koyama, Y, Takatsuka, I, Nakata, M, Tasumi, M 1988Raman and infrared-spectra of the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers of β-carotene-key bands distinguishing stretched or terminal-bent configurations from central-bent configurationsJ Raman Spectrosc193749CrossRefGoogle Scholar
  14. Lakshmi, KV, Reifler, MJ, Chisholm, DA, Wang, JY, Diner, BA, Brudvig, GW 2002Correlation of the cytochrome c550 content of cyanobacterial Photosystem II with the EPR properties of the oxygen-evolving complexPhotosynth Res72175189CrossRefGoogle Scholar
  15. Merlin, JC 1985Resonance Raman spectroscopy of carotenoids and carotenoid-containing systemsPure Appl Chem57785792Google Scholar
  16. Niyogi, KK 1999Photoprotection revisited: genetic and molecular approachesAnnu Rev Plant Phys50333359PubMedGoogle Scholar
  17. Pascal, A, Telfer, A, Barber, J, Robert, B 1999Fourier-transform resonance Raman spectra of cation carotenoid in Photosystem II reaction centersFEBS Lett4531114CrossRefPubMedGoogle Scholar
  18. Picorel, R, Holt, RE, Heald, R, Cotton, TM, Seibert, M 1991Stability of isolated bacterial and Photosystem-II reaction center complexes on Ag electrode surfaces-a surface-enhanced resonance Raman studyJ Am Chem Soc11328392843Google Scholar
  19. Robert, B 1990Resonance Raman studies of bacterial reaction centersBiochem Biophys Acta101799111Google Scholar
  20. Setlikova, E, Ritter, S, Hienerwadel, R, Kopecky, J, Komenda, J, Welte, W, Setlik, I 1995Purification of a Photosystem-II reaction center from a thermophilic cyanobacterium using immobilized metal affinity chromatographyPhotosynth Res43201211CrossRefGoogle Scholar
  21. Smith, PJ, Peterson, S, Masters, VM, Wydrzynski, T, Styring, S, Krausz, E, Pace, RJ 2002Magneto-optical measurements of the pigments in fully active Photosystem II core complexes from plantsBiochemistry4119811989PubMedGoogle Scholar
  22. Stewart, DH, Nixon, PJ, Diner, BA, Brudvig, GW 2000Assignment of the Q(y) absorbance bands of Photosystem II chromophores by low-temperature optical spectroscopy of wild-type and mutant reaction centersBiochemistry391458314594PubMedGoogle Scholar
  23. Telfer, A, Dhami, S, Bishop, SM, Phillips, D, Barber, J 1994β-Carotene quenches singlet oxygen formed by isolated Photosystem II reaction centersBiochemistry331446914474CrossRefPubMedGoogle Scholar
  24. Telfer, A, Frolov, D, Barber, J, Robert, B, Pascal, A 2003Oxidation of the two β-carotene molecules in the Photosystem II reaction centerBiochemistry4210081015CrossRefPubMedGoogle Scholar
  25. Tracewell, CA, Brudvig, GW 2003Two redox-active β-carotene molecules in Photosystem IIBiochemistry4291279136PubMedGoogle Scholar
  26. Tracewell, CA, Cua, A, Stewart, DH, Bocian, DF, Brudvig, GW 2001Characterization of carotenoid and chlorophyll photooxidation in Photosystem IIBiochemistry40193203CrossRefPubMedGoogle Scholar
  27. Tracewell, CA, Vrettos, JS, Bautista, JA, Frank, HA, Brudvig, GW 2001Carotenoid photooxidation in Photosystem IIArch Biochem Biophys3856169CrossRefPubMedGoogle Scholar
  28. Vasil’ev, S, Brudvig, GW, Bruce, D 2003The X-ray structure of Photosystem II reveals a novel electron transport pathway between P680, cytochrome b559 and the energy quenching cation, ChlZ+FEBS Lett543159163CrossRefPubMedGoogle Scholar
  29. Vrettos, JS, Stewart, DH, Paula, JC, Brudvig, GW 1999Low-temperature optical and resonance Raman spectra of a carotenoid cation radical in Photosystem IIJ Phys Chem B10364036406CrossRefGoogle Scholar
  30. Yruela, I, Tomas, R, Sanjuan, ML, Torrado, E, Aured, M, Picorel, R 1998The configuration of β-carotene in the Photosystem II reaction centerPhotochem Photobiol68729737CrossRefGoogle Scholar

Copyright information

© Springer 2005

Authors and Affiliations

  • Cara A. Tracewell
    • 1
  • Agnes Cua
    • 2
  • David F. Bocian
    • 2
  • Gary W. Brudvig
    • 1
  1. 1.Department of ChemistryYale UniversityNew HavenUSA
  2. 2.Department of ChemistryUniversity of CaliforniaRiversideUSA

Personalised recommendations