Synthesis and characterization of de novo designed peptides modelling the binding sites of [4Fe-4S] clusters in photosystem I

Biochim Biophys Acta. 2009 Aug;1787(8):995-1008. doi: 10.1016/j.bbabio.2009.03.007. Epub 2009 Mar 16.

Abstract

Photosystem I (PS I) converts the energy of light into chemical energy via transmembrane charge separation. The terminal electron transfer cofactors in PS I are three low-potential [4Fe-4S] clusters named F(X), F(A) and F(B), the last two are bound by the PsaC subunit. We have modelled the F(A) and F(B) binding sites by preparing two apo-peptides (maquettes), sixteen amino acids each. These model peptides incorporate the consensus [4Fe-4S] binding motif along with amino acids from the immediate environment of the iron-sulfur clusters F(A) and F(B). The [4Fe-4S] clusters were successfully incorporated into these model peptides, as shown by optical absorbance, EPR and Mössbauer spectroscopies. The oxidation-reduction potential of the iron-sulfur cluster in the F(A)-maquette is -0.44+/-0.03 V and in the F(B)-maquette is -0.47+/-0.03 V. Both are close to that of F(A) and F(B) in PS I and are considerably more negative than that observed for other [4Fe-4S] model systems described earlier (Gibney, B. R., Mulholland, S. E., Rabanal, F., and Dutton, P. L. Proc. Natl. Acad. Sci. U.S.A. 93 (1996) 15041-15046). Our optical data show that both maquettes can irreversibly bind to PS I complexes, where PsaC-bound F(A) and F(B) were removed, and possibly participate in the light-induced electron transfer reaction in PS I.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acid Sequence
  • Apoproteins / chemistry
  • Apoproteins / metabolism
  • Binding Sites
  • Chlorophyll / chemistry
  • Chlorophyll / metabolism
  • Electron Spin Resonance Spectroscopy
  • Iron-Sulfur Proteins / chemistry*
  • Iron-Sulfur Proteins / metabolism
  • Kinetics
  • Models, Molecular
  • Molecular Sequence Data
  • Oxidation-Reduction
  • Peptides / chemical synthesis
  • Peptides / chemistry*
  • Peptides / metabolism
  • Photosystem I Protein Complex / chemistry*
  • Photosystem I Protein Complex / metabolism
  • Protein Binding
  • Spectroscopy, Mossbauer

Substances

  • Apoproteins
  • Iron-Sulfur Proteins
  • Peptides
  • Photosystem I Protein Complex
  • photosystem I, psaB subunit
  • Chlorophyll
  • chlorophyll P 700