Abstract
Stark spectroscopy is a powerful technique to investigate the electrostatic interactions between pigments as well as between the pigments and the proteins in photosynthetic pigment–protein complexes. In this study, Stark spectroscopy has been used to determine two nonlinear optical parameters (polarizability change Tr(Δα) and static dipole-moment change |Δμ| upon photoexcitation) of isolated and of reconstituted LH1 complexes from the purple photosynthetic bacterium, Rhodospirillum (Rs.) rubrum. The integral LH1 complex was prepared from Rs. rubrum S1, while the reconstituted complex was assembled by addition of purified carotenoid (all-trans-spirilloxanthin) to the monomeric subunit of LH1 from Rs. rubrum S1. The reconstituted LH1 complex has its Qy absorption maximum at 878 nm. This is shifted to the blue by 3 nm in comparison to the isolated LH1 complex. The energy transfer efficiency from carotenoid to bacteriochlorophyll a (BChl a), which was determined by fluorescence excitation spectroscopy of the reconstituted LH1 complex, is increased to 40%, while the efficiency in the isolated LH1 complex is only 28%. Based on the differences in the values of Tr(Δα) and |Δμ|, between these two preparations, we can calculate the change in the electric field around the BChl a molecules in the two situations to be E Δ ≈ 3.4 × 105 [V/cm]. This change can explain the 3 nm wavelength shift of the Qy absorption band in the reconstituted LH1 complex.
Similar content being viewed by others
Abbreviations
- BChl a :
-
Bacteriochlorophyll a
- LDAO:
-
N,N-lauryl dimethyl aminooxide
- LH1:
-
Light-harvesting 1 complex
- RC:
-
Reaction centre
- Rs. rubrum S1:
-
Rhodospirillum rubrum strain S1
References
Akahane J, Rondonuwu FS, Fiedor L, Watanabe Y, Koyama Y (2004) Dependence of singlet-energy transfer on the conjugation length of carotenoids reconstituted into the LH1 complex from Rhodospirillum rubrum G9. Chem Phys Lett 393:184–191
Cogdell RJ, Crofts AR (1978) Analysis of the pigment content of an antenna pigment-protein complex from three strains of Rhodopseudomonas sphaeroides. Biochim Biophys Acta 502:409–416
Cogdell RJ, Andersson PA, Gillbro T (1992) Carotenoid singlet states and their involvement in photosynthetic light-harvesting pigments. J Photochem Photobiol B Biol 15:105–112
Cohen-Bazire G, Sistrom WR, Stanier RY (1957) Kinetic studies of pigment synthesis by non-sulfur purple bacteria. J Cell Comp Physiol 49:25–68
Davis CM, Bustamante PL, Loach PA (1995) Reconstitution of the bacterial core light-harvesting complexes of Rhodobacter sphaeroides and Rhodospirillum rubrum with isolated α- and β- polypeptides, bacteriochlorophyll a, and carotenoid. J Biol Chem 270:5793–5804
Fiedor L, Scheer H (2005) Trapping of an assembly intermediate of photosynthetic LH1 antenna beyond B820 subunit: significance for the assembly of photosynthetic LH1 antenna. J Biol Chem 280:20921–20926
Fiedor L, Akahane J, Koyama Y (2004) Carotenoid-induced cooperative formation of bacterial photosynthetic LH1 complex. Biochemistry 43:16487–16496
Frank HA (1999) Incorporation of carotenoids into reaction center and light-harvesting pigment-protein complexes. In: Frank HA, Young AJ, Britton G, Cogdell RJ (eds) The photochemistry of carotenoids, vol 8. Kluwer Academic Publishers, Dordrecht, The Netherlands, pp 235–244
Fujii R, Ishikawa T, Koyama Y, Taguchi M, Isobe Y, Nagae H, Watanabe Y (2001) Fluorescence spectroscopy of all-trans-anhydrorhodovibrin and spirilloxanthin: detection of the 1Bu- fluorescence. J Phys Chem A 105:5348–5355
Furuichi K, Sashima T, Koyama Y (2002) The first detection of the 3Ag- state in carotenoids using resonance-Raman excitation profiles. Chem Phys Lett 356:547–555
He Z, Sundström V, Pullerits T (2001) Excited states of carotenoid in LH2: an ab initio study. Chem Phys Lett 334:159–167
Kakitani Y, Akahane J, Ishii H, Sogabe H, Nagae H, Koyama Y (2007) Conjugation-length dependence of the T1 lifetimes of carotenoids free in solution and incorporated into the LH2, LH1, RC, and RC-LH1 complexes: possible mechanisms of triplet-energy dissipation. Biochemistry 46:2181–2197
Kjellberg P, He Z, Pullerits T (2003) Bacteriochlorophyll in electric field. J Phys Chem B 107:13737–13742
Liptay W (1974) Dipole moments and polarizabilities of molecules in excited electronic states. In: Lin EC (ed) Excited states, vol 1. Academic Press, New York, USA, pp 129–229
Nakagawa K, Suzuki S, Fujii R, Gardiner AT, Cogdell RJ, Nango M, Hashimoto H (2007) Electrostatic effect of surfactant molecules on bacteriochlorophyll a and carotenoid binding site in the LH1 complex isolated from Rhodospirillum rubrum S1 probed by Stark spectroscopy. Photosynth Res (in press)
Picorel R, Bélanger G, Gingras G (1983) Antenna holochrome B880 of Rhodospirillum rubrum S1: pigment, phospholipid, and polypeptide composition? Biochemistry 22:2491–2497
Rademaker H, Hoff AJ, van Grondelle R, Duysens LNM (1980) Carotenoid triplet yields in normal and deuterated Rhodospirillum rubrum. Biochim Biophys Acta 592:240–257
Roszak AW, McKendrick K, Gardiner AT, Mitchell IA, Isaacs NW, Cogdell RJ, Hashimoto H, Frank HA (2004) Protein regulation of carotenoid binding: gatekeeper and locking amino acid residues in reaction centers of Rhodobacter sphaeroides. Structure 12:765–773
Yanagi K, Hashimoto H, Gardiner AT, Cogdell RJ (2004) Stark spectroscopy on the LH2 complex from Rhodobacter sphaeroides strain G1C: frequency and temperature dependence. J Phys Chem B 108:10334–10339
Yanagi K, Shimizu M, Hashimoto H, Gardiner AT, Roszak AW, Cogdell RJ (2005) Local electrostatic field induced by the carotenoid bound to the reaction center of the purple photosynthetic bacterium Rhodobacter Sphaeroides. J Phys Chem B 109:992–998
Acknowledgements
This work was supported by the Grant-in-aid from the Japanese Ministry of Education, Culture, Sports, Science and Technology (Grants No. 17204026, No. 17654083). HH, RF, MN, ATG and RJC thank for the financial support from SICP/JST. HH also acknowledges for the support from PRESTO/JST. RJC and ATG thank for the financial support from BBSRC.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Nakagawa, K., Suzuki, S., Fujii, R. et al. Probing binding site of bacteriochlorophyll a and carotenoid in the reconstituted LH1 complex from Rhodospirillum rubrum S1 by Stark spectroscopy. Photosynth Res 95, 339–344 (2008). https://doi.org/10.1007/s11120-007-9261-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11120-007-9261-2