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Tunnelling readout of hydrogen-bonding-based recognition

Abstract

Hydrogen bonding has a ubiquitous role in electron transport1,2 and in molecular recognition, with DNA base pairing being the best-known example3. Scanning tunnelling microscope images4 and measurements of the decay of tunnel current as a molecular junction is pulled apart by the scanning tunnelling microscope tip5 are sensitive to hydrogen-bonded interactions. Here, we show that these tunnel-decay signals can be used to measure the strength of hydrogen bonding in DNA base pairs. Junctions that are held together by three hydrogen bonds per base pair (for example, guanine–cytosine interactions) are stiffer than junctions held together by two hydrogen bonds per base pair (for example, adenine–thymine interactions). Similar, but less pronounced effects are observed on the approach of the tunnelling probe, implying that attractive forces that depend on hydrogen bonds also have a role in determining the rise of current. These effects provide new mechanisms for making sensors that transduce a molecular recognition event into an electronic signal.

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Figure 1: Illustration of the STM measurements.
Figure 2: Tunnel-current decay curves.
Figure 3: A mechanical model of the tunnel gap.
Figure 4: Determination of elastic-interaction parameters and prediction of the tunnel decay curves.
Figure 5: Charge transfer, obtained from integration of the tunnel current decay curves, plotted as a function of set-point current for different molecular junctions.

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Acknowledgements

This work was supported by the DNA Sequencing Technology Program of the National Human Genome Research Institute (1 R21 HG004378-01), Arizona Technology Enterprises and the Biodesign Institute. The authors thank H. Liu for assistance with graphics and P. Krishnakumar for assistance with AFM measurements.

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Authors and Affiliations

Authors

Contributions

S.C. and J.H. carried out tunnelling measurements. A.K. carried out CAFM measurements. M.L. and O.S. performed the DFT calculations. P.Z. synthesized the materials. S.L. managed the experimental design and analysed the data.

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Correspondence to Stuart Lindsay.

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Competing interests

S.L., J.H. and P.Z. are inventors named on pending patent applications.

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Chang, S., He, J., Kibel, A. et al. Tunnelling readout of hydrogen-bonding-based recognition. Nature Nanotech 4, 297–301 (2009). https://doi.org/10.1038/nnano.2009.48

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