Relevance of the diastereotopic ligation of magnesium atoms of chlorophylls in Photosystem I

Teodor Silviu Balaban, Petra Fromme, Alfred R. Holzwarth, Norbert Krauß, Valentin I. Prokhorenko

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

The central magnesium (Mg) atoms of natural occurring tetrapyrroles such as chlorophylls (Chls) and bacteriochlorophylls (BChls) are typically five-coordinated, a fact which leads to the formation of diastereoisomers if the Mg-ligand bond is stable on the time scale of the observation method. This possibility has only been briefly addressed before in a CD-study of BChl c aggregates [T.S. Balaban, A.R. Holzwarth, K. Schaffner, J. Mol. Struct. 349 (1995) 183]. On the basis of the chlorophyll-protein complex photosystem I (PSI), which has recently been characterized by single crystal crystallography [P. Jordan, P. Fromme, H.T. Witt, O. Klukas, W. Saenger, N. Krauβ, Nature 411 (2001) 909], we find that chlorophyll a molecules are much more frequently bound by the protein matrix from one side (anti) than the other one (syn) in a ratio of 82:14, which corresponds to a significant ΔΔG value of 4.3 kJ/mol. Syn and anti denote the orientation of the Mg-ligand with respect to the 17-propionic acid esterified by phytol. Furthermore, by parallel sequence analysis we find that the binding sites for both syn and anti chlorophylls have been strongly conserved during evolution - a fact which stresses the nonrandom manner in which chlorophylls are bound by the apoprotein in antenna complexes, in order to exert efficiently their light harvesting function and energy funnelling. Most remarkably, all the syn chlorophylls are part of the inner core antenna system. Results from semiempirical quantum mechanical and detailed exciton coupling calculations allow us to speculate on the functional relevance of the diasteretopicity for PSI functioning.

Original languageEnglish
Pages (from-to)197-207
Number of pages11
JournalBiochimica et Biophysica Acta - Bioenergetics
Volume1556
Issue number2-3
DOIs
Publication statusPublished - Dec 2 2002

Fingerprint

Photosystem I Protein Complex
Chlorophyll
Magnesium
Ligation
Atoms
Phytol
Tetrapyrroles
Chlorophyll Binding Proteins
Antennas
Ligands
Bacteriochlorophylls
Jordan
Crystallography
Apoproteins
Sequence Analysis
Binding Sites
Observation
Single crystals
Light
Molecules

Keywords

  • Chlorophyll complex
  • Crystal structure
  • Diastereotopicity
  • Photosystem I
  • Sequence alignment

ASJC Scopus subject areas

  • Biophysics

Cite this

Relevance of the diastereotopic ligation of magnesium atoms of chlorophylls in Photosystem I. / Balaban, Teodor Silviu; Fromme, Petra; Holzwarth, Alfred R.; Krauß, Norbert; Prokhorenko, Valentin I.

In: Biochimica et Biophysica Acta - Bioenergetics, Vol. 1556, No. 2-3, 02.12.2002, p. 197-207.

Research output: Contribution to journalArticle

Balaban, Teodor Silviu ; Fromme, Petra ; Holzwarth, Alfred R. ; Krauß, Norbert ; Prokhorenko, Valentin I. / Relevance of the diastereotopic ligation of magnesium atoms of chlorophylls in Photosystem I. In: Biochimica et Biophysica Acta - Bioenergetics. 2002 ; Vol. 1556, No. 2-3. pp. 197-207.
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