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The origin of the “dark” absorption band near 675 nm in the purple bacterial core light-harvesting complex LH1: two-photon measurements of LH1 and its subunit B820

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Abstract

A comparative two-photon excitation spectroscopic study of the exciton structure of the core antenna complex (LH1) and its subunit B820 was carried out. LH1 and its subunit B820 were isolated from cells of the carotenoid-less mutant G9 of Rhodospirillum rubrum. The measurements were performed by two-photon pump-probe spectroscopy. Samples were excited by 70 fs pulses at 1390 nm at a frequency of 1 kHz. Photoinduced absorption changes were recorded in the spectral range from 780 to 1020 nm for time delays of the probe pulse relative to the pump pulse in the − 1.5 to 11 ps range. All measurements were performed at room temperature. Two-photon excitation caused bleaching of exciton bands (k = 0, k = ± 1) of the circular bacteriochlorophyll aggregate of LH1. In the case of the B820 subunit, two-photon excitation did not cause absorption changes in this spectral range. It is proposed that in LH1 upper exciton branch states are mixed with charge-transfer (CT) states. In B820 such mixing is absent, precluding two-photon excitation in this spectral region. Usually, CT states are optically “dark”, i.e., one photon-excitation forbidden. Thus, their investigation is rather complicated by conventional spectroscopic methods. Thus, our study provides a novel approach to investigate CT states and their interaction(s) with other excited states in photosynthetic light-harvesting complexes and other molecular aggregates.

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Abbreviations

(B)Chl:

(Bacterio)chlorophyll

CT:

Charge transfer

EET:

Excitation energy transfer

RC:

Reaction centre

LH1 (core-):

Light-harvesting complex 1

LH1-RC:

Ensemble consisting of LH1 and the RC

LH2:

Peripheral light-harvesting complex 2

B880:

Circular aggregate of BChl molecules in LH1

B850:

Circular aggregate of BChl molecules in LH2

B820:

Subunit of LH1

FWHM:

Full width at half maximum

O.U.:

Optical units

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Acknowledgements

This work has been supported in part by grants from the Russian Foundation for Basic Research (15-04-09289-a, 17-04-00929-a), and by the Czech Science Foundation (project P501/12/G055).

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Authors and Affiliations

  1. Belozersky Research Institute of Physico-Chemical Biology, MSU, Moscow, Russia

    Andrei Razjivin

  2. Institute of Basic Biological Problems, RAS, Pushchino, Moscow Region, Russia

    Alexander Solov’ev & Andrey Moskalenko

  3. Institute of Spectroscopy, RAS, Troitsk, Moscow, Russia

    Victor Kompanets & Sergey Chekalin

  4. Department of Chemical Physics and Optics, Charles University, Ke Karlovu 3, 121 16, Prague, Czech Republic

    Heiko Lokstein

Authors
  1. Andrei Razjivin
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  2. Alexander Solov’ev
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  3. Victor Kompanets
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  4. Sergey Chekalin
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  5. Andrey Moskalenko
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  6. Heiko Lokstein
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Correspondence to Andrei Razjivin.

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Razjivin, A., Solov’ev, A., Kompanets, V. et al. The origin of the “dark” absorption band near 675 nm in the purple bacterial core light-harvesting complex LH1: two-photon measurements of LH1 and its subunit B820. Photosynth Res 140, 207–213 (2019). https://doi.org/10.1007/s11120-018-0602-0

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