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Structural analysis of Cu(II) ligation to the 5′-GMP nucleotide by pulse EPR spectroscopy

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Abstract

Simple copper salts are known to denature poly d(GC). On the other hand, copper complexes of substituted 1,4,7,10,13-pentaazacyclohexadecane-14,16-dione are able to convert the right-handed B form of the same DNA sequence to the corresponding left-handed Z form. A research program was started in order to understand why Cu(II) as an aquated ion melts DNA and induces the conformational change to Z-DNA in the form of an azamacrocyclic complex. In this paper, we present a continuous wave and pulse electron paramagnetic resonance study of the mononucleotide model system Cu(II)–guanosine 5′-monophosphate . Pulse EPR methods like electron–nuclear double resonance and hyperfine sublevel correlation spectroscopy provide unique information about the electronic and geometric structure of this model system through an elaborate mapping of the hyperfine and nuclear quadrupole interactions between the unpaired electron of the Cu(II) ion and the magnetic nuclei of the nucleotide ligand. It was found that the Cu(II) ion is directly bound to N7 of guanosine 5′-monophosphate and indirectly bound via a water of hydration to a phosphate group. This set of experiments opens the way to more detailed structural characterization of specifically bound metal ions in a variety of nucleic acids of biological interest, in particular to understand the role of the metal–(poly)nucleotide interaction.

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Abbreviations

CW:

Continuous wave

DMSO:

Dimethyl sulfoxide

ENDOR:

Electron-nuclear double resonance

EPR:

Electron paramagnetic resonance

5′-GMP:

Guanosine 5′-monophosphate

HYSCORE:

Hyperfine sublevel correlation

Triflate:

Trifluoromethanesulfonate

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Acknowledgements

We thank R.K.O. Sigel and C. Finazzo for stimulating discussions. We thank ETH and the Swiss National Science Foundation for financial support.

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Authors and Affiliations

  1. Laboratory of Physical Chemistry, ETH Zurich, 8093, Zurich, Switzerland

    Maria Grazia Santangelo, Arthur Schweiger & George Mitrikas

  2. Institute of Inorganic Chemistry, University of Zurich, 8057, Zurich, Switzerland

    Alfredo Medina-Molner & Bernhard Spingler

  3. Institute of Materials Science, NCSR “Demokritos”, Aghia Paraskevi Attikis, 15310, Athens, Greece

    George Mitrikas

Authors
  1. Maria Grazia Santangelo
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  2. Alfredo Medina-Molner
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  3. Arthur Schweiger
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  4. George Mitrikas
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  5. Bernhard Spingler
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Corresponding authors

Correspondence to George Mitrikas or Bernhard Spingler.

Additional information

Arthur Schweiger died on 4 January 2006.

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Santangelo, M.G., Medina-Molner, A., Schweiger, A. et al. Structural analysis of Cu(II) ligation to the 5′-GMP nucleotide by pulse EPR spectroscopy. J Biol Inorg Chem 12, 767–775 (2007). https://doi.org/10.1007/s00775-007-0230-1

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  • DOI: https://doi.org/10.1007/s00775-007-0230-1

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