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Engineering nanometre-scale coherence in soft matter

Nature Chemistry volume 8, pages 941945 (2016) | Download Citation

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.

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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.

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Author notes

    • Chaoren Liu
    •  & Limin Xiang

    These authors contributed equally to this work

Affiliations

  1. Departments of Chemistry, Biochemistry and Physics, Duke University, Durham, North Carolina 27708, USA

    • Chaoren Liu
    • , Yuqi Zhang
    • , Peng Zhang
    •  & David N. Beratan
  2. Center of Biosensor & Bioelectronics, Biodesign Institute, Arizona State University, Tempe, Arizona 85287, USA

    • Limin Xiang
    • , Yueqi Li
    •  & Nongjian Tao

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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.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to David N. Beratan.

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DOI

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

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