Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Engineering nanometre-scale coherence in soft matter

Abstract

Electronic delocalization in redox-active polymers may be disrupted by the heterogeneity of the environment that surrounds each monomer. When the differences in monomer redox-potential induced by the environment are small (as compared with the monomer–monomer electronic interactions), delocalization persists. Here we show that guanine (G) runs in double-stranded DNA support delocalization over 4–5 guanine bases. The weak interaction between delocalized G blocks on opposite DNA strands is known to support partially coherent long-range charge transport. The molecular-resolution model developed here finds that the coherence among these G blocks follows an even–odd orbital-symmetry rule and predicts that weakening the interaction between G blocks exaggerates the resistance oscillations. These findings indicate how sequence can be exploited to change the balance between coherent and incoherent transport. The predictions are tested and confirmed using break-junction experiments. Thus, tailored orbital symmetry and structural fluctuations may be used to produce coherent transport with a length scale of multiple nanometres in soft-matter assemblies, a length scale comparable to that of small proteins.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Computed length-dependent resistance (Landauer analysis) for ds-5′CnGn3′ in which the resistance shows an odd–even oscillatory pattern, characteristic of coherent transport.
Figure 2: Schematic view of the guanine energy-difference distributions that produce delocalized versus localized states.
Figure 3: Cross-strand G-G overlaps and computed resistance for ds-5′CnGn3′ and ds-5′GnCn3′.
Figure 4: The measured resistances for ds-5′GnCn3′ (red curve) and for ds-5′CnGn3′ (black curve (data from ref. 9)) from break-junction experiments.

Similar content being viewed by others

References

  1. Ziman, J. M. Models of Disorder: The Theoretical Physics of Homogeneously Disordered Systems (Cambridge Univ. Press, 1979).

    Google Scholar 

  2. Collini, E. et al. Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature. Nature 463, 644–647 (2010).

    Article  CAS  Google Scholar 

  3. Hildner, R., Brinks, D., Nieder, J. B., Cogdell, R. J. & van Hulst, N. F. Quantum coherent energy transfer over varying pathways in single light-harvesting complexes. Science 340, 1448–1451 (2013).

    Article  CAS  Google Scholar 

  4. Engel, G. S. et al. Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems. Nature 446, 782–786 (2007).

    Article  CAS  Google Scholar 

  5. Muren, N. B., Olmon, E. D. & Barton, J. K. Solution, surface, and single molecule platforms for the study of DNA-mediated charge transport. Phys. Chem. Chem. Phys. 14, 13754–13771 (2012).

    Article  CAS  Google Scholar 

  6. Zhang, Y., Liu, C., Balaeff, A., Skourtis, S. S. & Beratan, D. N. Biological charge transfer via flickering resonance. Proc. Natl Acad. Sci. USA 111, 10049–10054 (2014).

    Article  CAS  Google Scholar 

  7. Hatcher, E., Balaeff, A., Keinan, S., Venkatramani, R. & Beratan, D. N. PNA versus DNA: effects of structural fluctuations on electronic structure and hole-transport mechanisms. J. Am. Chem. Soc. 130, 11752–11761 (2008).

    Article  CAS  Google Scholar 

  8. Venkatramani, R., Keinan, S., Balaeff, A. & Beratan, D. N. Nucleic acid charge transfer: black, white and gray. Coord. Chem. Rev. 255, 635–648 (2011).

    Article  CAS  Google Scholar 

  9. Xiang, L. et al. Intermediate tunnelling–hopping regime in DNA charge transport. Nature Chem. 7, 221–226 (2015).

    Article  CAS  Google Scholar 

  10. Buttiker, M. Coherent and sequential tunneling in series barriers. IBM J. Res. Dev. 32, 63–75 (1988).

    Article  Google Scholar 

  11. Giese, B. Long-distance electron transfer through DNA. Annu. Rev. Biochem. 71, 51–70 (2002).

    Article  CAS  Google Scholar 

  12. Renaud, N., Berlin, Y. A., Lewis, F. D. & Ratner, M. A. Between superexchange and hopping: an intermediate charge-transfer mechanism in poly(A)–poly(T) DNA hairpins. J. Am. Chem. Soc. 135, 3953–3963 (2013).

    Article  CAS  Google Scholar 

  13. Sato, N. Electrochemistry at Metal and Semiconductor Electrodes (Elsevier Science, 1998).

    Google Scholar 

  14. Caruso, T., Carotenuto, M., Vasca, E. & Peluso, A. Direct experimental observation of the effect of the base pairing on the oxidation potential of guanine. J. Am. Chem. Soc. 127, 15040–15041 (2005).

    Article  CAS  Google Scholar 

  15. Kittel, C. Introduction to Solid State Physics (Wiley, 2004).

    Google Scholar 

  16. Ryndyk, D. A. et al. Scanning tunneling spectroscopy of single DNA molecules. ACS Nano 3, 1651–1656 (2009).

    Article  CAS  Google Scholar 

  17. Yoshioka, Y. et al. Experimental and theoretical studies on the selectivity of GGG triplets toward one-electron oxidation in B-form DNA. J. Am. Chem. Soc. 121, 8712–8719 (1999).

    Article  CAS  Google Scholar 

  18. Chen, L., Hansen, T. & Franco, I. Simple and accurate method for time-dependent transport along nanoscale junctions. J. Phys. Chem. C 118, 20009–20017 (2014).

    Article  CAS  Google Scholar 

  19. Zhong, X. & Zhao, Y. Non-Markovian stochastic Schrödinger equation at finite temperatures for charge carrier dynamics in organic crystals. J. Chem. Phys. 138, 014111 (2013).

    Article  Google Scholar 

  20. Cheng, Y. C. & Silbey, R. J. Stochastic Liouville equation approach for the effect of noise in quantum computations. Phys. Rev. A 69, 052325 (2004).

    Article  Google Scholar 

  21. Zhong, X. & Zhao, Y. Charge carrier dynamics in phonon-induced fluctuation systems from time-dependent wavepacket diffusion approach. J. Chem. Phys. 135, 134110 (2011).

    Article  Google Scholar 

  22. Voityuk, A. A. Electronic couplings and on-site energies for hole transfer in DNA: systematic quantum mechanical/molecular dynamic study. J. Chem. Phys. 128, 115101 (2008).

    Article  Google Scholar 

  23. Gutiérrez, R. et al. Structural fluctuations and quantum transport through DNA molecular wires: a combined molecular dynamics and model Hamiltonian approach. New J. Phys. 12, 023022 (2010).

    Article  Google Scholar 

  24. Gutiérrez, R. et al. Charge transport through biomolecular wires in a solvent: bridging molecular dynamics and model Hamiltonian approaches. Phys. Rev. Lett. 102, 208102 (2009).

    Article  Google Scholar 

  25. Kubař, T. & Elstner, M. What governs the charge transfer in DNA? The role of DNA conformation and environment. J. Phys. Chem. B 112, 8788–8798 (2008).

    Article  Google Scholar 

  26. Basko, D. M. & Conwell, E. M. Effect of solvation on hole motion in DNA. Phys. Rev. Lett. 88, 098102 (2002).

    Article  CAS  Google Scholar 

  27. Renaud, N., Berlin, Y. A. & Ratner, M. A. Impact of a single base pair substitution on the charge transfer rate along short DNA hairpins. Proc. Natl Acad. Sci. USA 110, 14867–14871 (2013).

    Article  CAS  Google Scholar 

  28. Nitzan, A. Chemical Dynamics in Condensed Phases: Relaxation, Transfer and Reactions in Condensed Molecular Systems (Oxford Univ. Press, 2006).

    Google Scholar 

  29. Siebbeles, L. D. A. & Grozema, F. C. Charge and Exciton Transport through Molecular Wires (Wiley, 2011).

    Book  Google Scholar 

  30. Xu, B. & Tao, N. J. Measurement of single-molecule resistance by repeated formation of molecular junctions. Science 301, 1221–1223 (2003).

    Article  CAS  Google Scholar 

  31. Xu, B., Zhang, P., Li, X. & Tao, N. Direct conductance measurement of single DNA molecules in aqueous solution. Nano Lett. 4, 1105–1108 (2004).

    Article  CAS  Google Scholar 

  32. Guo, S., Hihath, J., Díez-Pérez, I. & Tao, N. Measurement and statistical analysis of single-molecule current–voltage characteristics, transition voltage spectroscopy, and tunneling barrier height. J. Am. Chem. Soc. 133, 19189–19197 (2011).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank the Office of Naval Research (N00014-11-1-0729) and the National Science Foundation (DMR-1413257) for support. We thank H. Yan and S. Jiang for assistance with the non-denaturing PAGE gel experiments.

Author information

Authors and Affiliations

Authors

Contributions

C.L., Y.Z., P.Z. and D.N.B. conceived, conducted and analysed the simulations in consultation with the experimental team. L.X., Y.L. and N.-J.T. designed and conducted the break-junction experiments in consultation with the theoretical team. The two teams collaborated intensively in formulating the key molecular designs, analysing the data and writing the paper.

Corresponding author

Correspondence to David N. Beratan.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 4101 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, C., Xiang, L., Zhang, Y. et al. Engineering nanometre-scale coherence in soft matter. Nature Chem 8, 941–945 (2016). https://doi.org/10.1038/nchem.2545

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.2545

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing