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Effect of backbone flexibility on charge transfer rates in peptide nucleic acid duplexes.

Publication ,  Journal Article
Wierzbinski, E; de Leon, A; Yin, X; Balaeff, A; Davis, KL; Rapireddy, S; Venkatramani, R; Keinan, S; Ly, DH; Madrid, M; Beratan, DN; Achim, C ...
Published in: Journal of the American Chemical Society
June 2012

Charge transfer (CT) properties are compared between peptide nucleic acid structures with an aminoethylglycine backbone (aeg-PNA) and those with a γ-methylated backbone (γ-PNA). The common aeg-PNA is an achiral molecule with a flexible structure, whereas γ-PNA is a chiral molecule with a significantly more rigid structure than aeg-PNA. Electrochemical measurements show that the CT rate constant through an aeg-PNA bridging unit is twice the CT rate constant through a γ-PNA bridging unit. Theoretical calculations of PNA electronic properties, which are based on a molecular dynamics structural ensemble, reveal that the difference in the CT rate constant results from the difference in the extent of backbone fluctuations of aeg- and γ-PNA. In particular, fluctuations of the backbone affect the local electric field that broadens the energy levels of the PNA nucleobases. The greater flexibility of the aeg-PNA gives rise to more broadening, and a more frequent appearance of high-CT rate conformations than in γ-PNA.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

June 2012

Volume

134

Issue

22

Start / End Page

9335 / 9342

Related Subject Headings

  • Peptides
  • Nucleic Acids
  • Molecular Structure
  • Glycine
  • General Chemistry
  • Electron Transport
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

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Wierzbinski, E., de Leon, A., Yin, X., Balaeff, A., Davis, K. L., Rapireddy, S., … Waldeck, D. H. (2012). Effect of backbone flexibility on charge transfer rates in peptide nucleic acid duplexes. Journal of the American Chemical Society, 134(22), 9335–9342. https://doi.org/10.1021/ja301677z
Wierzbinski, Emil, Arnie de Leon, Xing Yin, Alexander Balaeff, Kathryn L. Davis, Srinivas Rapireddy, Ravindra Venkatramani, et al. “Effect of backbone flexibility on charge transfer rates in peptide nucleic acid duplexes.Journal of the American Chemical Society 134, no. 22 (June 2012): 9335–42. https://doi.org/10.1021/ja301677z.
Wierzbinski E, de Leon A, Yin X, Balaeff A, Davis KL, Rapireddy S, et al. Effect of backbone flexibility on charge transfer rates in peptide nucleic acid duplexes. Journal of the American Chemical Society. 2012 Jun;134(22):9335–42.
Wierzbinski, Emil, et al. “Effect of backbone flexibility on charge transfer rates in peptide nucleic acid duplexes.Journal of the American Chemical Society, vol. 134, no. 22, June 2012, pp. 9335–42. Epmc, doi:10.1021/ja301677z.
Wierzbinski E, de Leon A, Yin X, Balaeff A, Davis KL, Rapireddy S, Venkatramani R, Keinan S, Ly DH, Madrid M, Beratan DN, Achim C, Waldeck DH. Effect of backbone flexibility on charge transfer rates in peptide nucleic acid duplexes. Journal of the American Chemical Society. 2012 Jun;134(22):9335–9342.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

June 2012

Volume

134

Issue

22

Start / End Page

9335 / 9342

Related Subject Headings

  • Peptides
  • Nucleic Acids
  • Molecular Structure
  • Glycine
  • General Chemistry
  • Electron Transport
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences