Photosynthesis Research

, Volume 111, Issue 1–2, pp 193–204 | Cite as

Self-assembly and energy transfer in artificial light-harvesting complexes of bacteriochlorophyll c with astaxanthin

  • J. Alster
  • T. Polívka
  • J. B. Arellano
  • P. Hříbek
  • F. Vácha
  • J. Hála
  • J. Pšenčík
Regular Paper

Abstract

Chlorosomes, the light-harvesting antennae of green photosynthetic bacteria, are based on large aggregates of bacteriochlorophyll molecules. Aggregates with similar properties to those in chlorosomes can also be prepared in vitro. Several agents were shown to induce aggregation of bacteriochlorophyll c in aqueous environments, including certain lipids, carotenes, and quinones. A key distinguishing feature of bacteriochlorophyll c aggregates, both in vitro and in chlorosomes, is a large (>60 nm) red shift of their Qy absorption band compared with that of the monomers. In this study, we investigate the self-assembly of bacteriochlorophyll c with the xanthophyll astaxanthin, which leads to the formation of a new type of complexes. Our results indicate that, due to its specific structure, astaxanthin molecules competes with bacteriochlorophylls for the bonds involved in the aggregation, thus preventing the formation of any significant red shift compared with pure bacteriochlorophyll c in aqueous buffer. A strong interaction between both the types of pigments in the developed assemblies, is manifested by a rather efficient (~40%) excitation energy transfer from astaxanthin to bacteriochlorophyll c, as revealed by fluorescence excitation spectroscopy. Results of transient absorption spectroscopy show that the energy transfer is very fast (<500 fs) and proceeds through the S2 state of astaxanthin.

Keywords

Light-harvesting Chlorosomes Self-assembly Bacteriochlorophyll aggregates Astaxanthin 

Notes

Acknowledgments

This study was supported by the Czech Ministry of Education, Youth and Sports (projects MSM0021620835, MSM6007665808, AV0Z50510513), Czech Science Foundation (projects 206/09/0375, 202/09/H041, 202/09/1330), and Spanish Ministry of Science and Innovation (AVCR-CSIC joint project 2008CZ0004). The authors would like to thank Ivana Hunalova, Frantisek Matousek, and Anita Zupcanova for their help with pigment isolation.

Supplementary material

11120_2011_9670_MOESM1_ESM.pdf (21 kb)
Figure S1: Correction of the absorption spectra of BChl c-astaxanthin assemblies for light-scattering. Spectra were measured at a position further (solid line) and closer (dotted line) to the detector of the spectrophotometer. The difference between them were rescaled to fit the uncorrected spectra above 850 nm which reflected the scattering part of the spectra (dashed line). The corrected spectrum (dash-dot line) was obtained by subtracting the scattering part from the solid line. (PDF 21 kb)
11120_2011_9670_MOESM2_ESM.pdf (27 kb)
Figure S2: Transient absorption spectra of BChl c assemblies with astaxanthin (molar ratio 0.35:1 astaxanthin-to-BChl c, blue lines) and BChl c dimers with lecithin (green lines). All spectra were measured at 2.1 ps after selective excitation of BChl c at 710 nm. The inset shows an enlargement of the 450-600 nm region. The inverted absorption spectrum of astaxanthin in the assemblies, reproduced from Fig. 3 and scaled to fit, is shown for the sake of comparison (black line, inset). The difference spectrum (red line) reveals a shift of the Qy band of BChl c and a small negative signal in the 450-600 nm region. This small signal can be caused entirely by a change in the BChl–BChl excitonic interaction between the two samples, or by an additional excitonic interaction between BChl c and astaxanthin resulting in bleaching of the astaxanthin upon BChl c excitation. The spectra were smoothed by a 10 point (± 2.5 nm) adjacent averaging. (PDF 28 kb)

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Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • J. Alster
    • 1
  • T. Polívka
    • 2
    • 3
  • J. B. Arellano
    • 4
  • P. Hříbek
    • 2
  • F. Vácha
    • 2
    • 3
  • J. Hála
    • 1
  • J. Pšenčík
    • 1
    • 2
  1. 1.Faculty of Mathematics and PhysicsCharles UniversityPrahaCzech Republic
  2. 2.Institute of Physical BiologyUniversity of South BohemiaNové HradyCzech Republic
  3. 3.Biology CentreAcademy of Sciences of the Czech RepublicČeské BudějoviceCzech Republic
  4. 4.Instituto de Recursos Naturales y Agrobiología de Salamanca (IRNASA-CSIC)SalamancaSpain

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