Excitation energy trapping and dissipation by Ni-substituted bacteriochlorophyll a in reconstituted LH1 complexes from Rhodospirillum rubrum

J Phys Chem B. 2013 Sep 26;117(38):11260-71. doi: 10.1021/jp4020977. Epub 2013 Jul 26.

Abstract

Bacteriochlorophyll a with Ni(2+) replacing the central Mg(2+) ion was used as an ultrafast excitation energy dissipation center in reconstituted bacterial LH1 complexes. B870, a carotenoid-less LH1 complex, and B880, an LH1 complex containing spheroidene, were obtained via reconstitution from the subunits isolated from chromatophores of Rhodospirillum rubrum . Ni-substituted bacteriochlorophyll a added to the reconstitution mixture partially substituted the native pigment in both forms of LH1. The excited-state dynamics of the reconstituted LH1 complexes were probed by femtosecond pump-probe transient absorption spectroscopy in the visible and near-infrared spectral region. Spheroidene-binding B880 containing no excitation dissipation centers displayed complex dynamics in the time range of 0.1-10 ps, reflecting internal conversion and intersystem crossing in the carotenoid, exciton relaxation in BChl complement, and energy transfer from carotenoid to the latter. In B870, some aggregation-induced excitation energy quenching was present. The binding of Ni-BChl a to both B870 and B880 resulted in strong quenching of the excited states with main deexcitation lifetime of ca. 2 ps. The LH1 excited-state lifetime could be modeled with an intrinsic decay time constant in Ni-substituted bacteriochlorophyll a of 160 fs. The presence of carotenoid in LH1 did not influence the kinetics of energy trapping by Ni-BChl unless the carotenoid was directly excited, in which case the kinetics was limited by a slower carotenoid S1 to bacteriochlorophyll energy transfer.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bacterial Proteins / chemistry*
  • Bacterial Proteins / metabolism
  • Bacteriochlorophyll A / chemistry*
  • Carotenoids / chemistry
  • Energy Transfer
  • Ions / chemistry
  • Light-Harvesting Protein Complexes / chemistry*
  • Light-Harvesting Protein Complexes / metabolism
  • Microscopy, Atomic Force
  • Nickel / chemistry*
  • Protochlorophyllide / chemistry
  • Protochlorophyllide / metabolism
  • Rhodospirillum rubrum / metabolism*
  • Spectrometry, Fluorescence
  • Time Factors

Substances

  • Bacterial Proteins
  • Bacteriochlorophyll A
  • Ions
  • Light-Harvesting Protein Complexes
  • holochrome protein, Rhodospirillum rubrum
  • spheroidene
  • Protochlorophyllide
  • Carotenoids
  • Nickel