The electrical conductance of ds-DNA duplexes containing 8 to 14 base pairs modified at both ends with a -(CH 2 ) 6 -SH linker was measured in a buffered aqueous solution using electrochemically controlled distance tunneling spectroscopy. The tunneling experiment with selfcomplementary 5′-(GC) n -3′-(CH 2 ) 6 -SH (n=4-7) duplexes attached covalently to a gold STM tip and a Au(111) electrode shows a wide distribution of currents independent of the ds-DNA length. The voltage-induced horizontal orientation of ds-DNA within the junction results in decreased electrical conductance. The lower currents are also observed for ds-DNA molecules containing a single CA base mismatch.
TOC imageKeywords DNA conductivity; scanning tunneling distance spectroscopy; electrochemical STM The nature of electrical transport along the DNA duplex is important in understanding DNA damage in vivo and in exploring the possible use of DNA in molecular electronics and direct detection of DNA hybridization. The ongoing scientific debate places DNA molecules in all possible electrical conductivity ranges -from an insulator to a proximity induced superconductor. [1][2][3][4] It is apparent that the experimental conditions, including the nature of the contact between the electrode and the molecule, as well as the orientation and the structure In particular, the DNA structure and flexibility depend significantly on the counter-ion and on the electrostatic interactions between the electrical contact and the molecule. 12 Thus, it is important to measure the electrical properties of single DNA molecules while rigorously controlling the electrochemical parameters of the experiment.We report here the electrochemical tunneling distance spectroscopy measurements of electrical conductance of series of ds-DNA molecules modified with a -C 6 -SH linker attached to 3′ ends of DNA in 10 mM phosphate buffer + 100 mM sodium chloride solution. This approach allows us to control the orientation of ds-DNA molecule within the STM junction by means of electrostatic interactions between the molecule and the electrochemically polarized metal contact.In a tunneling distance spectroscopy with electrochemical gate, shown schematically in figure 1A, the STM tip is first brought into close proximity of the Au(111) electrode at the initial set-point current, i 0 . The STM tip is then lifted while the x-y position is kept constant and the current-distance (i-s) curve is recorded. This experimental procedure follows the method previously used by Haiss et al. 13 to measure electrical conductivity of α,ω-alkanedithiol molecules bridging the STM gap. A similar method of measuring of molecule conductance, starting with the formation of a mechanical contact between the STM tip and a substrate, was previously introduced by Tao et al. 14 Figure 1B shows a typical current-distance (i-s) transient recorded in the absence of preadsorbed molecules on the Au(111) surface. The initial position of STM tip versus Au(111) surface is established by using a set-point current, i 0 =4nA,...