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The role of axial ligands for the structure and function of chlorophylls

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Abstract

We have studied the effect of axial ligation of chlorophyll and bacteriochlorophyll using density functional calculations. Eleven different axial ligands have been considered, including models of histidine, aspartate/glutamate, asparagine/glutamine, serine, tyrosine, methionine, water, the protein backbone, and phosphate. The native chlorophylls, as well as their cation and anion radical states and models of the reaction centres P680 and P700, have been studied and we have compared the geometries, binding energies, reduction potentials, and absorption spectra. Our results clearly show that the chlorophylls strongly prefer to be five-coordinate, in accordance with available crystal structures. The axial ligands decrease the reduction potentials, so they cannot explain the high potential of P680. They also redshift the Q band, but not enough to explain the occurrence of red chlorophylls. However, there is some relation between the axial ligands and their location in the various photosynthetic proteins. In particular, the intrinsic reduction potential of the second molecule in the electron transfer path is always lower than that of the third one, a feature that may prevent back-transfer of the electron.

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Abbreviations

Backb:

Amino acid backbone

BChl:

Bacteriochlorophyll

BDE:

Bond dissociation energy

BP86:

Becke’s 1988 gradient corrected exchange functional, combined with Perdew’s 1986 correlation functional

Chl:

Chlorophyll

COSMO:

Conductor-like screening model

LHC:

Light-harvesting complex

Pheo:

Pheophytin

Phos:

Phosphate

PSI:

Photosystem I

PSII:

Photosystem II

RC:

Reaction centre

RI:

Resolution-of-the-identity approximation

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Acknowledgements

This investigation was supported by grants from the Swedish Research Council and by computer resources of Lunarc at Lund University.

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Authors and Affiliations

  1. Department of Theoretical Chemistry, Lund University, Chemical Centre, P.O. Box 124, 221 00, Lund, Sweden

    Jimmy Heimdal, Kasper P. Jensen, Ajitha Devarajan & Ulf Ryde

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  1. Jimmy Heimdal
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  2. Kasper P. Jensen
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  3. Ajitha Devarajan
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  4. Ulf Ryde
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Correspondence to Ulf Ryde.

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Heimdal, J., Jensen, K.P., Devarajan, A. et al. The role of axial ligands for the structure and function of chlorophylls. J Biol Inorg Chem 12, 49–61 (2007). https://doi.org/10.1007/s00775-006-0164-z

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  • DOI: https://doi.org/10.1007/s00775-006-0164-z

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