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Concerted dynamics of metallo-base pairs in an A/B-form helical transition

Author

Listed:
  • Olivia P. Schmidt

    (University of Zurich)

  • Simon Jurt

    (University of Zurich)

  • Silke Johannsen

    (University of Zurich)

  • Ashkan Karimi

    (University of Zurich)

  • Roland K. O. Sigel

    (University of Zurich)

  • Nathan W. Luedtke

    (University of Zurich)

Abstract

Metal-mediated base pairs expand the repertoire of nucleic acid structures and dynamics. Here we report solution structures and dynamics of duplex DNA containing two all-natural C-HgII-T metallo base pairs separated by six canonical base pairs. NMR experiments reveal a 3:1 ratio of well-resolved structures in dynamic equilibrium. The major species contains two (N3)T-HgII-(N3)C base pairs in a predominantly B-form helix. The minor species contains (N3)T-HgII-(N4)C base pairs and greater A-form characteristics. Ten-fold different 1J coupling constants (15N,199Hg) are observed for (N3)C-HgII (114 Hz) versus (N4)C-HgII (1052 Hz) connectivities, reflecting differences in cytosine ionization and metal-bonding strengths. Dynamic interconversion between the two types of C-HgII-T base pairs are coupled to a global conformational exchange between the helices. These observations inspired the design of a repetitive DNA sequence capable of undergoing a global B-to-A-form helical transition upon adding HgII, demonstrating that C-HgII-T has unique switching potential in DNA-based materials and devices.

Suggested Citation

  • Olivia P. Schmidt & Simon Jurt & Silke Johannsen & Ashkan Karimi & Roland K. O. Sigel & Nathan W. Luedtke, 2019. "Concerted dynamics of metallo-base pairs in an A/B-form helical transition," Nature Communications, Nature, vol. 10(1), pages 1-11, December.
  • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-12440-x
    DOI: 10.1038/s41467-019-12440-x
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