Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly

Natalia E. Powers-Riggs, Xiaobing Zuo, Ryan M. Young, Michael R. Wasielewski

Research output: Contribution to journalArticle

Abstract

Guanine-quadruplex (G-quadruplex) assemblies provide a useful platform for studying the spatial, structural, and photophysical effects of intermolecular interactions. Coupling a single guanine moiety to terrylenediimide (TDI)- A chromophore with a large extended π-surface-produces a structure (GTDI) that assembles in plate-like tetramers, with the potential of undergoing tunable π-stacking. At high concentrations (3 × 10-3 M), GTDI self-assembles into a nearly monodisperse G-quadruplex structure of 16 layers, with strong π-overlap between TDI moieties, observed by small- A nd wide-angle X-ray scattering. Transient absorption spectroscopy reveals that excitation of TDI in the G-quadruplex results in symmetry-breaking charge separation to form ion pairs within the structure, owing to the strong π-overlap enforced by the hydrogen-bonding. These assemblies yield important insights into the interplay of noncovalent interactions in the assembly of ordered chromophoric arrays.

Original languageEnglish
Pages (from-to)17512-17516
Number of pages5
JournalJournal of the American Chemical Society
Volume141
Issue number44
DOIs
Publication statusPublished - Nov 6 2019

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G-Quadruplexes
Guanine
Hydrogen Bonding
Chromophores
X ray scattering
Absorption spectroscopy
Spectrum Analysis
Hydrogen bonds
X-Rays
Ions

ASJC Scopus subject areas

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

Cite this

Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly. / Powers-Riggs, Natalia E.; Zuo, Xiaobing; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 141, No. 44, 06.11.2019, p. 17512-17516.

Research output: Contribution to journalArticle

Powers-Riggs, Natalia E. ; Zuo, Xiaobing ; Young, Ryan M. ; Wasielewski, Michael R. / Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 44. pp. 17512-17516.
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