DNA as helical ruler

Exciton-coupled circular dichroism in DNA conjugates

Frederick D. Lewis, Ligang Zhang, Xiaoyang Liu, Xiaobing Zuo, David M. Tiede, Hai Long, George C Schatz

Research output: Contribution to journalArticle

102 Citations (Scopus)

Abstract

The structure and properties of oligonucleotide conjugates possessing stilbenedicarboxamide chromophores at both ends of a poly(dA):poly(dT) base-pair domain of variable length have been investigated using a combination of spectroscopic and computational methods. These conjugates form capped hairpin structures in which one stilbene serves as a hairpin linker and the other as a hydrophobic end-cap. The capping stilbene stabilizes the hairpin structures by ca. 2 kcal/mol, making possible the formation of a stable folded structure containing a single A:T base pair. Exciton coupling between the stilbene chromophores has little effect on the absorption bands of capped hairpins. However, exciton-coupled circular dichroism (EC-CD) can be observed for capped hairpins possessing as many as 11 base pairs. Both the sign and intensity of the EC-CD spectrum are sensitive to the number of base pairs separating the stilbene chromophores, as a consequence of the distance and angular dependence of exciton coupling. Calculated spectra obtained using a static vector model based on canonical B-DNA are in good agreement with the experimental spectra. Molecular dynamics simulations show that conformational fluctuations of the capped hairpins result in large deviations of the averaged spectra in both the positive and negative directions. These results demonstrate for the first time the ability of B-DNA to serve as a helical ruler for the study of electronic interactions between aligned chromophores. Furthermore, they provide important tests for atomistic theoretical models of DNA.

Original languageEnglish
Pages (from-to)14445-14453
Number of pages9
JournalJournal of the American Chemical Society
Volume127
Issue number41
DOIs
Publication statusPublished - Oct 19 2005

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Stilbenes
Dichroism
Chromophores
Circular Dichroism
Base Pairing
Excitons
DNA
B-Form DNA
Oligonucleotides
Molecular Dynamics Simulation
Computational methods
Molecular dynamics
Absorption spectra
Theoretical Models
LDS 751
Computer simulation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

DNA as helical ruler : Exciton-coupled circular dichroism in DNA conjugates. / Lewis, Frederick D.; Zhang, Ligang; Liu, Xiaoyang; Zuo, Xiaobing; Tiede, David M.; Long, Hai; Schatz, George C.

In: Journal of the American Chemical Society, Vol. 127, No. 41, 19.10.2005, p. 14445-14453.

Research output: Contribution to journalArticle

Lewis, Frederick D. ; Zhang, Ligang ; Liu, Xiaoyang ; Zuo, Xiaobing ; Tiede, David M. ; Long, Hai ; Schatz, George C. / DNA as helical ruler : Exciton-coupled circular dichroism in DNA conjugates. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 41. pp. 14445-14453.
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