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      Gate-controlled conductance switching in DNA

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          Abstract

          Extensive evidence has shown that long-range charge transport can occur along double helical DNA, but active control (switching) of single-DNA conductance with an external field has not yet been demonstrated. Here we demonstrate conductance switching in DNA by replacing a DNA base with a redox group. By applying an electrochemical (EC) gate voltage to the molecule, we switch the redox group between the oxidized and reduced states, leading to reversible switching of the DNA conductance between two discrete levels. We further show that monitoring the individual conductance switching allows the study of redox reaction kinetics and thermodynamics at single molecular level using DNA as a probe. Our theoretical calculations suggest that the switch is due to the change in the energy level alignment of the redox states relative to the Fermi level of the electrodes.

          Abstract

          Thanks to its base stacking structure, DNA can behave as an electric wire, but external control of its electronic properties has not been achieved yet. Here, the authors show that DNA conductance can be switched electrochemically when a DNA base is replaced by the redox molecule anthraquinone.

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          Most cited references75

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          The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals

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            Measurement of single-molecule resistance by repeated formation of molecular junctions.

            The conductance of a single molecule connected to two gold electrodes was determined by repeatedly forming thousands of gold-molecule-gold junctions. Conductance histograms revealed well-defined peaks at integer multiples of a fundamental conductance value, which was used to identify the conductance of a single molecule. The resistances near zero bias were 10.5 +/- 0.5, 51 +/- 5, 630 +/- 50, and 1.3 +/- 0.1 megohms for hexanedithiol, octanedithiol, decanedithiol, and 4,4' bipyridine, respectively. The tunneling decay constant (betaN) for N-alkanedithiols was 1.0 +/- 0.1 per carbon atom and was weakly dependent on the applied bias. The resistance and betaN values are consistent with first-principles calculations.
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              Density functionals with broad applicability in chemistry.

              Although density functional theory is widely used in the computational chemistry community, the most popular density functional, B3LYP, has some serious shortcomings: (i) it is better for main-group chemistry than for transition metals; (ii) it systematically underestimates reaction barrier heights; (iii) it is inaccurate for interactions dominated by medium-range correlation energy, such as van der Waals attraction, aromatic-aromatic stacking, and alkane isomerization energies. We have developed a variety of databases for testing and designing new density functionals. We used these data to design new density functionals, called M06-class (and, earlier, M05-class) functionals, for which we enforced some fundamental exact constraints such as the uniform-electron-gas limit and the absence of self-correlation energy. Our M06-class functionals depend on spin-up and spin-down electron densities (i.e., spin densities), spin density gradients, spin kinetic energy densities, and, for nonlocal (also called hybrid) functionals, Hartree-Fock exchange. We have developed four new functionals that overcome the above-mentioned difficulties: (a) M06, a hybrid meta functional, is a functional with good accuracy "across-the-board" for transition metals, main group thermochemistry, medium-range correlation energy, and barrier heights; (b) M06-2X, another hybrid meta functional, is not good for transition metals but has excellent performance for main group chemistry, predicts accurate valence and Rydberg electronic excitation energies, and is an excellent functional for aromatic-aromatic stacking interactions; (c) M06-L is not as accurate as M06 for barrier heights but is the most accurate functional for transition metals and is the only local functional (no Hartree-Fock exchange) with better across-the-board average performance than B3LYP; this is very important because only local functionals are affordable for many demanding applications on very large systems; (d) M06-HF has good performance for valence, Rydberg, and charge transfer excited states with minimal sacrifice of ground-state accuracy. In this Account, we compared the performance of the M06-class functionals and one M05-class functional (M05-2X) to that of some popular functionals for diverse databases and their performance on several difficult cases. The tests include barrier heights, conformational energy, and the trend in bond dissociation energies of Grubbs' ruthenium catalysts for olefin metathesis. Based on these tests, we recommend (1) the M06-2X, BMK, and M05-2X functionals for main-group thermochemistry and kinetics, (2) M06-2X and M06 for systems where main-group thermochemistry, kinetics, and noncovalent interactions are all important, (3) M06-L and M06 for transition metal thermochemistry, (4) M06 for problems involving multireference rearrangements or reactions where both organic and transition-metal bonds are formed or broken, (5) M06-2X, M05-2X, M06-HF, M06, and M06-L for the study of noncovalent interactions, (6) M06-HF when the use of full Hartree-Fock exchange is important, for example, to avoid the error of self-interaction at long-range, (7) M06-L when a local functional is required, because a local functional has much lower cost for large systems.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                20 February 2017
                2017
                : 8
                : 14471
                Affiliations
                [1 ]Biodesign Center for Biosensors and Bioelectronics, Biodesign Institute, Arizona State University , Tempe, Arizona 85287, USA
                [2 ]School of Molecular Sciences, Arizona State University , Tempe, Arizona 85287, USA
                [3 ]Department of Chemistry, The Pennsylvania State University, Fayette , The Eberly Campus, 2201 University Drive, Lemont Furnace, Pennsylvania 15456, USA
                [4 ]Department of Chemistry, Northwestern University , Evanston, Illinois 60208, USA
                [5 ]School of Electrical, Computer and Energy Engineering, Arizona State University , Tempe, Arizona 85287, USA
                Author notes
                Article
                ncomms14471
                10.1038/ncomms14471
                5321735
                28218275
                1d61163e-b787-4b34-a100-2f9785696ad9
                Copyright © 2017, The Author(s)

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 13 July 2016
                : 03 January 2017
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