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