Molecular rectifier composed of DNA with high rectification ratio enabled by intercalation

[en] The predictability, diversity and programmability of DNA make it a leading candidate for the design of functional electronic devices that use single molecules, yet its electron transport properties have not been fully elucidated. This is primarily because of a poor understanding of how the structure of DNA determines its electron transport. Here, we demonstrate a DNA-based molecular rectifier constructed by site-specific intercalation of small molecules (coralyne) into a custom-designed 11-base-pair DNA duplex. Measured current–voltage curves of the DNA–coralyne molecular junction show unexpectedly large rectification with a rectification ratio of about 15 at 1.1 V, a counter-intuitive finding considering the seemingly symmetrical molecular structure of the junction. A non-equilibrium Green’s function-based model— parameterized by density functional theory calculations—revealed that the coralyne-induced spatial asymmetry in the electron state distribution caused the observed rectification. This inherent asymmetry leads to changes in the coupling of the molecular HOMO−1 level to the electrodes when an external voltage is applied, resulting in an asymmetric change in transmission.

Disciplines :

Chemistry
Physics

Author, co-author :

Guo, Cunlan ^✱

Wang, Kun ^✱

Zerah-Harush, Elinor

Hamill, Joseph ; Université de Liège - ULiège > Molecular Systems (MolSys)

Wang, Bin

Dubi, Yonatan

Xu, Bingqian

^✱ These authors have contributed equally to this work.

Language :

English

Title :

Molecular rectifier composed of DNA with high rectification ratio enabled by intercalation

Publication date :

2016

Journal title :

Nature Chemistry

ISSN :

1755-4330

eISSN :

1755-4349

Publisher :

Nature Research

Volume :

Issue :

Pages :

484–490

Peer reviewed :

Peer Reviewed verified by ORBi

Available on ORBi :

since 01 April 2026

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174

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200

Bibliography

Ratner, M. A brief history of molecular electronics. Nature Nanotech. 8, 378-381 (2013).
Tao, N. J. Electron transport in molecular junctions. Nature Nanotech. 1, 173-181 (2006).
Aradhya, S. V. & Venkataraman, L. Single-molecule junctions beyond electronic transport. Nature Nanotech. 8, 399-410 (2013).
Di Ventra, M. & Pershin, Y. V. Spin physics: DNA spintronics sees the light. Nature Nanotech. 6, 198-199 (2011).
Genereux, J. C. & Barton, J. K. Molecular electronics: DNA charges ahead. Nature Chem. 1, 106-107 (2009).
Livshits, G. I. et al. Long-range charge transport in single G-quadruplex DNA molecules. Nature Nanotech. 9, 1040-1046 (2014).
Dekker, C. & Ratner, M. A. Electronic properties of DNA. Phys. World 14, 29-33 (2001).
Mallajosyula, S. S. & Pati, S. K. Toward DNA conductivity: a theoretical perspective. J. Phys. Chem. Lett. 1, 1881-1894 (2010).
Giese, B. et al. Direct observation of hole transfer through DNA by hopping between adenine bases and by tunnelling. Nature 412, 318-320 (2001).
Lewis, F. D. et al. Direct measurement of hole transport dynamics in DNA. Nature 406, 51-53 (2000).
Xiang, L. et al. Intermediate tunnelling-hopping regime in DNA charge transport. Nature Chem. 7, 221-226 (2015).
Wang, K. et al. Structure determined charge transport in single DNA molecule break junctions. Chem. Sci. 5, 3425-3431 (2014).
Joshua, H. et al. Effects of cytosine methylation on DNA charge transport. J. Phys. Condens. Matter 24, 164204 (2012).
Tsutsui, M. et al. Electrical detection of single methylcytosines in a DNA oligomer. J. Am. Chem. Soc. 133, 9124-9128 (2011).
Liu, H. et al. Electronic enhancement effect of copper modification of base pairs on the conductivity of DNA. J. Phys. Chem. C 115, 22547-22556 (2011).
Liu, S. et al. Direct conductance measurement of individual metallo-DNA duplexes within single-molecule break junctions. Angew. Chem. Int. Ed. 50, 8886-8890 (2011).
Aviram, A. & Ratner, M. A. Molecular rectifiers. Chem. Phys. Lett. 29, 277-283 (1974).
Ashwell, G. J., Tyrrell, W. D. & Whittam, A. J. Molecular rectification: selfassembled monolayers in which donor-(π-bridge)-acceptor moieties are centrally located and symmetrically coupled to both gold electrodes. J. Am. Chem. Soc. 126, 7102-7110 (2004).
Nijhuis, C. A., Reus, W. F. & Whitesides, G. M. Mechanism of rectification in tunneling junctions based on molecules with asymmetric potential drops. J. Am. Chem. Soc. 132, 18386-18401 (2010).
Díez-Pérez, I. et al. Rectification and stability of a single molecular diode with controlled orientation. Nature Chem. 1, 635-641 (2009).
Elbing, M. et al. A single-molecule diode. Proc. Natl Acad. Sci. USA 102, 8815-8820 (2005).
Batra, A. et al. Tuning rectification in single-molecular diodes. Nano Lett. 13, 6233-6237 (2013).
Yoon, H. J. et al. Rectification in tunneling junctions: 2,2′-bipyridyl-terminated n-alkanethiolates. J. Am. Chem. Soc. 136, 17155-17162 (2014).
Yee, S. K. et al. Inverse rectification in donor-acceptor molecular heterojunctions. ACS Nano 5, 9256-9263 (2011).
Wang, K. et al. Measurement and understanding of single-molecule break junction rectification caused by asymmetric contacts. J. Chem. Phys. 141, 054712 (2014).
Xu, B. & Tao, N. Measurement of single-molecule resistance by repeated formation of molecular junctions. Science 301, 1221-1223 (2003).
Zhou, J., Chen, F. & Xu, B. Fabrication and electronic characterization of single molecular junction devices: a comprehensive approach. J. Am. Chem. Soc. 131, 10439-10446 (2009).
Persil, Ö. et al. Assembly of an antiparallel homo-adenine DNA duplex by smallmolecule binding. J. Am. Chem. Soc. 126, 8644-8645 (2004).
Polak, M. & Hud, N. V. Complete disproportionation of duplex poly(dT)·poly (dA) into triplex poly(dT)·poly(dA)·poly(dT) and poly(dA) by coralyne. Nucleic Acids Res. 30, 983-992 (2002).
Ren, J. & Chaires, J. B. Sequence and structural selectivity of nucleic acid binding ligands. Biochemistry 38, 16067-16075 (1999).
Stadler, R., Geskin, V. & Cornil, J. A theoretical view of unimolecular rectification. J. Phys. Condens. Matter 20, 374105 (2008).
Capozzi, B. et al. Single-molecule diodes with high rectification ratios through environmental control. Nature Nanotech. 10, 522-527 (2015).
Huang, C. et al. Break junction under electrochemical gating: testbed for singlemolecule electronics. Chem. Soc. Rev. 44, 889-901 (2015).
Capozzi, B. et al. Tunable charge transport in single-molecule junctions via electrolytic gating. Nano Lett. 14, 1400-1404 (2014).
Genereux, J. C., Wuerth, S. M. & Barton, J. K. Single-step charge transport through DNA over long distances. J. Am. Chem. Soc. 133, 3863-3868 (2011).
Tan, B. et al. Charge transport in DNA nanowires connected to carbon nanotubes. Phys. Rev. B 92, 075429 (2015).
Brisker-Klaiman, D. & Peskin, U. Coherent elastic transport contribution to currents through ordered DNA molecular junctions. J. Phys. Chem. C 114, 19077-19082 (2010).
Cuniberti, G. et al. in Charge Migration in DNA (ed. Chakraborty, T.) 1-20 (Springer, 2007).
Yi, J. Conduction of DNA molecules: a charge-ladder model. Phys. Rev. B 68, 193103 (2003).
Grib, N. et al. Distance-dependent coherent charge transport in DNA: crossover from tunneling to free propagation. J. Biophys. Chem. 1, 77-85 (2010).
Jortner, J. et al. Superexchange mediated charge hopping in DNA. J. Phys. Chem. A 106, 7599-7606 (2002).
Voityuk, A. A. et al. Energetics of hole transfer in DNA. Chem. Phys. Lett. 324, 430-434 (2000).
Voityuk, A. A. et al. Electronic coupling for charge transfer and transport in DNA. J. Phys. Chem. B 104, 9740-9745 (2000).
Perrin, M. L. et al. Large tunable image-charge effects in single-molecule junctions. Nature Nanotech. 8, 282-287 (2013).
Xu, B. & Dubi, Y. Negative differential conductance in molecular junctions: an overview of experiment and theory. J. Phys. Condens. Matter 27, 263202 (2015).
Verzijl, C. J. O., Seldenthuis, J. S. & Thijssen, J. M. Applicability of the wide-band limit in DFT-based molecular transport calculations. J. Chem. Phys. 138, 094102 (2013).
Vanderbilt, D. & Louie, S. G. A Monte-Carlo simulated annealing approach to optimization over continuous variables. J. Comput. Phys. 56, 259-271 (1984).
Nowak, A. M. & McCreery, R. L. In situ Raman spectroscopy of bias-induced structural changes in nitroazobenzene molecular electronic junctions. J. Am. Chem. Soc. 126, 16621-16631 (2004).
Kornilovitch, P. E., Bratkovsky, A. M. & Stanley Williams, R. Current rectification by molecules with asymmetric tunneling barriers. Phys. Rev. B 66, 165436 (2002).
Liu, R. et al. Organometallic molecular rectification. J. Chem. Phys. 124, 024718 (2006).