where he has worked since 1993. He received his Ph.D. in Solid State Physics in 1982 and his D.Sc. in Theoretical Physics in 1998. His research covers solid state physics, the physics of liquids, theory of adsorption, many-particle physics and the theory of electrochemical electron transfer. His present research is focused on the theory of electron tunneling in bridged electrochemical contacts. He is the author or co-author of more than 60 publications in scientific journals. Qijin Chi received his Ph.D. degree in analytical and physical chemistry in 1994 from the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. After having spent one year as a DFG postdoctoral fellow at Tübingen University, Germany, and two years as a JSPS postdoctoral fellow in Tokyo, Japan, he joined the Department of Chemistry at Technical University of Denmark in 1998. He is currently a lektor (associate professor) in chemistry. Qijin Chi also studied molecular biology and biochemistry (2000-2003) at the Johns Hopkins University School of Medicine. His research interests include biological nanomaterials, electrochemistry, surface self-assembled chemistry, and biophysics. He has authored four patents, over fifty research articles, and several book chapters. Tim Albrecht graduated in chemistry at the University of Essen in 2000. He received a Ph.D. with Prof. P. Hildebrandt at the Max-Planck Institute for Radiation Chemistry (now Bioinorganic Chemistry) in Muelheim/ Germany for studies on interfacial charge transfer processes of heme proteins using spectroelectrochemistry (SE(R)RS) and electrochemical STM. He held a Marie-Curie fellowship 2004-2006 whilst working in Prof. J. Ulstrup's group and became a lecturer in Physical Chemistry at Imperial College London in 2006. His research interests include (bio)electrochemistry, charge transport through individual molecules, and electrode/nanopore architectures in single-biomolecule sensing. He has published 14 research articles, 2 book chapters, and filed 2 patent applications. Palle Skovhus Jensen obtained his M.Sc. degree in 2006 at Technical University of Denmark and is presently a Ph.D. student in Prof. J. Ulstrup's group. His research includes interfacial electrochemistry, electrochemical STM and AFM of redox metalloproteins, extending to catalysis of bioelectrochemical processes by molecular scale metallic nanoparticles. He is the co-author of several research articles in these areas.

We report high-resolution measurements of the forces between two atomically smooth solid surfaces across a film of 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid, for film thickness down to a single ion diameter. For films thinner than approximately 2 nm oscillatory structural forces are observed as the surface separation decreases and pairs of ion layers are squeezed out of the film. Strikingly, measurements of the shear stress of the ionic liquid film reveal low friction coefficients which are 1-2 orders of magnitude smaller than for analogous films of non-polar molecular liquids, including standard hydrocarbon lubricants, up to ca. 1 MPa pressure. We attribute this to the geometric and charge characteristics of the ionic liquid: the irregular shapes of the ions lead to a low shear stress, while the strong coulombic interactions between the ions and the charged confining surfaces lead to a robust film which is maintained between the shearing surfaces when pressure is applied across the film.

We report on the fabrication and characterization of a DNA nanopore detector with integrated tunneling electrodes. Functional tunneling devices were identified by tunneling spectroscopy in different solvents and then used in proof-of-principle experiments demonstrating, for the first time, concurrent tunneling detection and ionic current detection of DNA molecules in a nanopore platform. This is an important step toward ultrafast DNA sequencing by tunneling.

Electron transport through semiconductor and metallic nanoscale structures, molecular monolayers, and single molecules connected to external electrodes display rectification, switch, and staircase functionality of potential importance in future miniaturization of electronic devices. Common to most reported systems is, however, ultrahigh vacuum and/or cryogenic working conditions. Here we introduce a single-molecule device concept based on a class of robust redox active transition metal (Os(II)/(III)) complexes inserted between the working electrode and tip in an electrochemical scanning tunneling microscope (in situ STM). This configuration resembles a single-molecule transistor, where the reference electrode corresponds to the gate electrode. It operates at room temperature in a condensed matter (here aqueous) environment. Amplification on-off ratios up to 50 are found when the redox level is brought into the energy window between the Fermi levels of the electrodes by the overpotential ("gate voltage"). The current-voltage characteristics for two Os(II)/(III) complexes have been characterized systematically and supported by theoretical frames based on molecular charge transport theory.

Experimental data and theoretical notions are presented for 6-[1'-(6-mercapto-hexyl)-[4,4']bipyridinium]-hexane-1-thiol iodide (6V6) "wired" between a gold electrode surface and tip in an in situ scanning tunneling microscopy configuration. The viologen group can be used to "gate" charge transport across the molecular bridge through control of the electrochemical potential and consequently the redox state of the viologen moiety. This gating is theoretically considered within the framework of superexchange and coherent two-step notions for charge transport. It is shown here that the absence of a maximum in the Itunneling versus electrode potential relationship can be fitted by a "soft" gating concept. This arises from large configurational fluctuations of the molecular bridge linked to the gold contacts by flexible chains. This view is incorporated in a formalism that is well-suited for data analysis and reproduces in all important respects the 6V6 data for physically sound values of the appropriate parameters. This study demonstrates that fluctuations of isolated configurationally "soft" molecules can dominate charge transport patterns and that theoretical frameworks for compact monolayers may not be directly applied under such circumstances.

We used electrochemical scanning tunneling microscopy (STM) and spectroscopy (STS) to elucidate the mechanism of electron transport through individual pyridyl-based Os complexes. Our tunneling data obtained by two-dimensional electrochemical STS and STM imaging lead us to the conclusion that electron transport occurs by thermally activated hopping. The conductance enhancement around the redox potential of the complex, which is reminiscent of switching and transistor characterics in electronics, is reflected both in the STM imaging contrast and directly in the tunneling current. The latter shows a biphasic distance dependence, in line with a two-step electron hopping process. Under conditions where the substrate/molecule electron transfer (ET) step is dominant in determining the overall tunneling current, we determined the conductance of an individual Os complex to be 9 nS (Vbias = 0.1 V). We use theoretical approaches to connect the single-molecule conductance with electrochemical kinetics data obtained from monolayer experiments. While the latter leave some controversy regarding the degree of electronic coupling, our results suggest that electron transport occurs in the adiabatic limit of strong electronic coupling. Remarkably, and in contrast to established ET theory, the redox-mediated tunneling current remains strongly distance dependent due to the electronic coupling, even in the adiabatic limit. We exploit this feature and apply it to electrochemical single-molecule conductance data. In this way, we attempt to paint a unified picture of electrochemical charge transport at the single-molecule and monolayer levels.

Molecular redox levels can be used to modulate tunneling currents through single or small numbers of molecules and induce molecular electronic device function. While most of these devices require cryogenic conditions, room temperature operation has been demonstrated by using electrochemical gating in aqueous environments. The latter have, however, serious shortcomings with a view on their relatively high volatility and narrow stability ranges in terms of potential. Here we report the first-time use of an ionic liquid, 1-butyl-3-methylimidazoliumhexafluorophosphate (BMI), as an electrochemical gate in a Scanning Tunneling Microscope (STM) configuration. Ionic liquids are known to have a very low vapor pressure, and accessible potential ranges are in principle large, up to 6 V. In a proof-of-principle experiment, we show how a heteroleptic redox-active Os bisterpyridine complex (Ossac) can be brought to exhibit both transistor and diode function in this novel environment at room temperature. This renders ionic liquids an attractive gating medium for configurations where back-gating is difficult to implement (e.g., break-junction techniques) or experimental conditions prohibit the use of aqueous or organic electrolyte media (vacuum or high temperatures). From an applied perspective, they represent a step toward solid-state molecular electronics with electrochemical gating.

Redox molecules with equilibrium potentials suitable for electrochemical control offer perspectives in nanoscale and single-molecule electronics. This applies to molecular but also towards higher sophistication such as transistor or diode function. Most recent nanoscale or single-molecule functional systems are, however, fraught with operational limitations such as cryogenic temperatures and ultra-high vacuum, or lack of electrochemical potential control. We report here cyclic voltammetry (CV) using single-crystal Au(111)- and Pt(111)-electrodes and electrochemical in situ scanning tunnelling microscopy (STM) of a class of Os(II)/(III)- and Co(II)/(III)-complexes, the former novel molecular electronics. The complexes are robust, with ligand groups suitable for linking the complexes to the Au(111)- and Pt(111)-surfaces via N- and S-donor atoms. The data reflect monolayer behaviour. Interfacial ET of the Os-complexes is fast, kET(0) > or = 10(6) s(-1), while the Co-complex reacts much more slowly, kET(0) approximately (1-3) x 10(3) s(-1). In STM of the Os-complexes shows a maximum in the tunnelling current/overpotential relation at constant bias voltage with up to 50-fold current rise. The peak position systematically the bias voltage and equilibrium potential, in keeping with theoretical frames for two-step electron transfer (ET) of in situ STM of redox molecules. The molecular conductivity behaves broadly similarly. The Co-complex also shows a tunnelling spectroscopic feature but much weaker than the Os-complexes. This can be ascribed much smaller interfacial ET rate constant, again caused by large intramolecular nuclear reorganization and weak electronic coupling to the substrate electrode. Overall the has mapped the properties of target molecules needed for stable electronic switching, possible importance in molecular electronics towards the single-molecule level, in room temperature condensed matter environment.