Long-range vibrational dynamics are directed by Watson-Crick base-pairing in duplex DNA

Gordon Hithell, Daniel J. Shaw, Paul M. Donaldson, Gregory M. Greetham, Michael Towrie, Glenn A. Burley, Anthony W. Parker, Neil T. Hunt

Research output: Contribution to journalArticlepeer-review

29 Citations (Scopus)
87 Downloads (Pure)

Abstract

Ultrafast two-dimensional infrared (2D-IR) spectroscopy of a 15-mer A-T DNA duplex in solution has revealed structure-dependent vibrational coupling and energy transfer processes linking bases with the sugar-phosphate backbone. Duplex melting induces significant changes in the positions of off-diagonal peaks linking carbonyl and ring-stretching vibrational modes of the adenine and thymine bases with vibrations of the phosphate group and phosphodiester linkage. These indicate that Watson-Crick hydrogen bonding and helix formation leads to a unique vibrational coupling arrangement of base vibrational modes with those of the phosphate unit. Based on observations from time-resolved 2D-IR data, we conclude that rapid energy transfer processes occur between base and backbone, mediated by additional modes located on the deoxyribose moiety within the same nucleotide. These relaxation dynamics are insensitive to duplex melting, showing that efficient intramo-lecular energy relaxation to the solvent via the phosphate groups is the key to excess energy dissipation in both single and double-stranded DNA.
Original languageEnglish
JournalJournal of Physical Chemistry B
Early online date15 Apr 2016
DOIs
Publication statusE-pub ahead of print - 15 Apr 2016

Keywords

  • long-range vibrational dynamics
  • Watson-Crick Base-Pairing
  • duplex DNA
  • 2d-ir spectroscopy

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