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Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid.

Publication ,  Journal Article
Venkatramani, R; Davis, KL; Wierzbinski, E; Bezer, S; Balaeff, A; Keinan, S; Paul, A; Kocsis, L; Beratan, DN; Achim, C; Waldeck, DH
Published in: Journal of the American Chemical Society
January 2011

We present evidence for a near-resonant mechanism of charge transfer in short peptide nucleic acid (PNA) duplexes obtained through electrochemical, STM break junction (STM-BJ), and computational studies. A seven base pair (7-bp) PNA duplex with the sequence (TA)(3)-(XY)-(TA)(3) was studied, in which XY is a complementary nucleobase pair. The experiments showed that the heterogeneous charge transfer rate constant (k(0)) and the single-molecule conductance (σ) correlate with the oxidation potential of the purine base in the XY base pair. The electrochemical measurements showed that the enhancement of k(0) is independent, within experimental error, of which of the two PNA strands contains the purine base of the XY base pair. 7-bp PNA duplexes with one or two GC base pairs had similar measured k(0) and conductance values. While a simple superexchange model, previously used to rationalize charge transfer in single stranded PNA (Paul et al. J. Am. Chem. Soc. 2009, 131, 6498-6507), describes some of the experimental observations, the model does not explain the absence of an enhancement in the experimental k(0) and σ upon increasing the G content in the duplexes from one to two. Moreover, the superexchange model is not consistent with other studies (Paul et al. J. Phys. Chem. B 2010, 114, 14140), that showed a hopping charge transport mechanism is likely important for PNA duplexes longer than seven base pairs. A quantitative computational analysis shows that a near-resonant charge transfer regime, wherein a mix of superexchange and hopping mechanisms are expected to coexist, can rationalize all of the experimental results.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

January 2011

Volume

133

Issue

1

Start / End Page

62 / 72

Related Subject Headings

  • Peptide Nucleic Acids
  • Models, Molecular
  • General Chemistry
  • Electron Transport
  • Electrochemistry
  • Electric Conductivity
  • Base Sequence
  • Base Pairing
  • 40 Engineering
  • 34 Chemical sciences
 

Citation

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Venkatramani, R., Davis, K. L., Wierzbinski, E., Bezer, S., Balaeff, A., Keinan, S., … Waldeck, D. H. (2011). Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid. Journal of the American Chemical Society, 133(1), 62–72. https://doi.org/10.1021/ja107622m
Venkatramani, Ravindra, Kathryn L. Davis, Emil Wierzbinski, Silvia Bezer, Alexander Balaeff, Shahar Keinan, Amit Paul, et al. “Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid.Journal of the American Chemical Society 133, no. 1 (January 2011): 62–72. https://doi.org/10.1021/ja107622m.
Venkatramani R, Davis KL, Wierzbinski E, Bezer S, Balaeff A, Keinan S, et al. Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid. Journal of the American Chemical Society. 2011 Jan;133(1):62–72.
Venkatramani, Ravindra, et al. “Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid.Journal of the American Chemical Society, vol. 133, no. 1, Jan. 2011, pp. 62–72. Epmc, doi:10.1021/ja107622m.
Venkatramani R, Davis KL, Wierzbinski E, Bezer S, Balaeff A, Keinan S, Paul A, Kocsis L, Beratan DN, Achim C, Waldeck DH. Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid. Journal of the American Chemical Society. 2011 Jan;133(1):62–72.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

January 2011

Volume

133

Issue

1

Start / End Page

62 / 72

Related Subject Headings

  • Peptide Nucleic Acids
  • Models, Molecular
  • General Chemistry
  • Electron Transport
  • Electrochemistry
  • Electric Conductivity
  • Base Sequence
  • Base Pairing
  • 40 Engineering
  • 34 Chemical sciences