Sequential energy transfer driven by monoexponential dynamics in a biohybrid light-harvesting complex 2 (LH2)

Abstract

Enhancing the light-harvesting potential of antenna components in a system of solar energy conversion is an important topic in the field of artificial photosynthesis. We constructed a biohybrid light-harvesting complex 2 (LH2) engineered from Rhodobacter sphaeroides IL106 strain. An artificial fluorophore Alexa Fluor 647 maleimide (A647) was attached to the LH2 bearing cysteine residue at the N-terminal region (LH2-NC) near B800 bacteriochlorophyll a (BChl) assembly. The A647-attached LH2-NC conjugate (LH2-NC-A647) preserved the integrity of the intrinsic chromophores, B800- and B850-BChls, and carotenoids. Femtosecond transient absorption spectroscopy revealed that the sequential energy transfer A647 → B800 → B850 occurs at time scale of 9–10 ps with monoexponential dynamics in micellar and lipid bilayer systems. A B800-removed conjugate (LH2-NC[B800(−)]-A647) exhibited a significant decrease in energy transfer efficiency in the micellar system; however, surprisingly, direct energy transfer from A647 to B850 was observed at a rate comparable to that for LH2-NC-A647. This result implies that the energy transfer pathway is modified after B800 removal. The results obtained suggested that a LH2 complex is a potential platform for construction of biohybrid light-harvesting materials with simple energy transfer dynamics through the site-selective attachment of the external antennae and the modifiable energy-funnelling pathway.

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Acknowledgements

This work was supported by JSPS KAKENHI Grant Numbers JP26107002, JP16J00627, and 17H05255 in Scientific Research on Innovative Areas “Photosynergetics” and also by JP18H05160 and JP18H05180 in “Innovations for Light-Energy Conversion”. T. D. thanks The Ogasawara Foundation for the Promotion of Science and Engineering. T. D. thanks Mr. Naoto Mizutani for his excellent assistance with the experiments in the early stages of this work.

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Correspondence to Yutaka Nagasawa or Takehisa Dewa.

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Yoneda, Y., Kato, D., Kondo, M. et al. Sequential energy transfer driven by monoexponential dynamics in a biohybrid light-harvesting complex 2 (LH2). Photosynth Res 143, 115–128 (2020). https://doi.org/10.1007/s11120-019-00677-y

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Keywords

  • Biohybrid antenna
  • Light-harvesting complex 2 (LH2)
  • Sequential energy transfer
  • Monoexponential dynamics
  • Lipid bilayer
  • Femtosecond transient absorption spectroscopy