Face-to-face and edge-to-face π-π interactions in a synthetic DNA hairpin with a stilbenediether linker

Martin Egli*, Valentina Tereshko, Garib N. Mushudov, Ruslan Sanishvili, Xiaoyang Liu, Frederick D. Lewis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

57 Scopus citations


Synthetic conjugates possessing bis(2-hydroxyethyl)stilbene-4,4′ -diether linkers (Sd2) form the most stable DNA hairpins reported to date. Factors that affect stability are length and flexibility of the linkers and π-stacking of the stilbene moiety on the adjacent base pair. The crystal structure of the hairpin d(GT4G)-Sd2-d(CA4C) was determined at 1.5 Å resolution. The conformations of the two molecules in the asymmetric unit differ both in the linker and the stem portions. One of them shows a planar stilbene that is stacked on the adjacent G:C base pair. The other displays considerable rotation between the phenyl rings and an unprecedented edge-to-face orientation of stilbene and base pair. The observation of considerable variations in the conformation of the Sd moiety in the crystal structure allows us to exclude restriction of motion as the reason for the absence of Sd photoisomerization in the hairpins. Conformational differences in the stem portion of the two hairpin molecules go along with different Mg2+ binding modes. Most remarkable among them is the sequence-specific coordination of a metal ion in the narrow A-tract minor groove. The crystal structure provides unequivocal evidence that a fully hydrated Mg2+ ion can penetrate the narrow A-tract minor groove, causing the groove to further contract. Overall, the structural data provide a better understanding of the origins of hairpin stability and their photochemical behavior in solution.

Original languageEnglish (US)
Pages (from-to)10842-10849
Number of pages8
JournalJournal of the American Chemical Society
Issue number36
StatePublished - Sep 10 2003

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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