Skip to main content
Journal cover image

Biological charge transfer via flickering resonance.

Publication ,  Journal Article
Zhang, Y; Liu, C; Balaeff, A; Skourtis, SS; Beratan, DN
Published in: Proceedings of the National Academy of Sciences of the United States of America
July 2014

Biological electron-transfer (ET) reactions are typically described in the framework of coherent two-state electron tunneling or multistep hopping. However, these ET reactions may involve multiple redox cofactors in van der Waals contact with each other and with vibronic broadenings on the same scale as the energy gaps among the species. In this regime, fluctuations of the molecular structures and of the medium can produce transient energy level matching among multiple electronic states. This transient degeneracy, or flickering electronic resonance among states, is found to support coherent (ballistic) charge transfer. Importantly, ET rates arising from a flickering resonance (FR) mechanism will decay exponentially with distance because the probability of energy matching multiple states is multiplicative. The distance dependence of FR transport thus mimics the exponential decay that is usually associated with electron tunneling, although FR transport involves real carrier population on the bridge and is not a tunneling phenomenon. Likely candidates for FR transport are macromolecules with ET groups in van der Waals contact: DNA, bacterial nanowires, multiheme proteins, strongly coupled porphyrin arrays, and proteins with closely packed redox-active residues. The theory developed here is used to analyze DNA charge-transfer kinetics, and we find that charge-transfer distances up to three to four bases may be accounted for with this mechanism. Thus, the observed rapid (exponential) distance dependence of DNA ET rates over distances of ≲ 15 Å does not necessarily prove a tunneling mechanism.

Duke Scholars

Altmetric Attention Stats
Dimensions Citation Stats

Published In

Proceedings of the National Academy of Sciences of the United States of America

DOI

EISSN

1091-6490

ISSN

0027-8424

Publication Date

July 2014

Volume

111

Issue

28

Start / End Page

10049 / 10054

Related Subject Headings

  • Oxidation-Reduction
  • Nanowires
  • Models, Chemical
  • Kinetics
  • Electron Transport
  • DNA, Bacterial
  • Bacteria
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Zhang, Y., Liu, C., Balaeff, A., Skourtis, S. S., & Beratan, D. N. (2014). Biological charge transfer via flickering resonance. Proceedings of the National Academy of Sciences of the United States of America, 111(28), 10049–10054. https://doi.org/10.1073/pnas.1316519111
Zhang, Yuqi, Chaoren Liu, Alexander Balaeff, Spiros S. Skourtis, and David N. Beratan. “Biological charge transfer via flickering resonance.Proceedings of the National Academy of Sciences of the United States of America 111, no. 28 (July 2014): 10049–54. https://doi.org/10.1073/pnas.1316519111.
Zhang Y, Liu C, Balaeff A, Skourtis SS, Beratan DN. Biological charge transfer via flickering resonance. Proceedings of the National Academy of Sciences of the United States of America. 2014 Jul;111(28):10049–54.
Zhang, Yuqi, et al. “Biological charge transfer via flickering resonance.Proceedings of the National Academy of Sciences of the United States of America, vol. 111, no. 28, July 2014, pp. 10049–54. Epmc, doi:10.1073/pnas.1316519111.
Zhang Y, Liu C, Balaeff A, Skourtis SS, Beratan DN. Biological charge transfer via flickering resonance. Proceedings of the National Academy of Sciences of the United States of America. 2014 Jul;111(28):10049–10054.
Journal cover image

Published In

Proceedings of the National Academy of Sciences of the United States of America

DOI

EISSN

1091-6490

ISSN

0027-8424

Publication Date

July 2014

Volume

111

Issue

28

Start / End Page

10049 / 10054

Related Subject Headings

  • Oxidation-Reduction
  • Nanowires
  • Models, Chemical
  • Kinetics
  • Electron Transport
  • DNA, Bacterial
  • Bacteria