Electrochemistry and bioelectrochemistry towards the single-molecule level: Theoretical notions and systems

Jingdong Zhang, Qijin Chi, Tim Albrecht, AM Kuznetsov, Mikala Grubb, AG Hansen, Hainer Wackerbarth, Anne Christina Welinder, Jens Ulstrup

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Abstract

Surface structures controlled at the nanometer and single-molecule levels, with functions crucially determined by interfacial electron transfer (ET) are broadly reported in recent years, with different kinds of electrochemically controlled nanoscale/single molecule systems. One is the broad class of metallic and semiconductor-based nanoparticles, nano-arrays, nanotubes, and nanopits. Others are based on self-assembled molecular monolayers. The latter extend to bioelectrochemical systems with redox metalloproteins and DNA-based molecules as targets. We overview here some recent achievements in areas of interfacial electrochemical ET systems, mapped to the nanoscale and single-molecule levels. Focus is on both experimental and theoretical studies in our group. Systems addressed are organized monolayers of redox active transition metal complexes, and metalloproteins and metalloenzymes on single-crystal Au(111)-electrode surfaces. These systems have been investigated by voltammetry, spectroscopy, microcantilever technology, and scanning probe microscopy. A class of Os-complexes has shown suitable as targets for electrochemical in situ scanning tunnelling microscopy (STM), with close to single-molecule scanning tunnelling spectroscopic (STS) features. Mapping of redox metalloproteins from the three major classes, i.e. blue copper proteins, heme proteins, and iron-sulfur proteins, at the monolayer and single-molecule levels have also been achieved. In situ STM and spectroscopy of redox molecules and biomolecules have been supported by new theoretical frames, which extend established theory of interfacial electrochemical ET. The electrochemical nanoscale and single-molecule systems discussed are compared with other recent nanoscale and single-molecule systems with conspicuous device-like properties, particularly unimolecular rectifiers and single-molecule transistors. Both of these show analogies to electrochemical in situ STM features of redox molecules and biomolecules
Original languageEnglish
JournalELECTROCHIMICA ACTA 50
Volume50 Sp.Iss.
Issue number15
Pages (from-to)3143-3159
ISSN0013-4686
Publication statusPublished - 2005

Cite this

Zhang, J., Chi, Q., Albrecht, T., Kuznetsov, AM., Grubb, M., Hansen, AG., Wackerbarth, H., Welinder, A. C., & Ulstrup, J. (2005). Electrochemistry and bioelectrochemistry towards the single-molecule level: Theoretical notions and systems. ELECTROCHIMICA ACTA 50, 50 Sp.Iss.(15), 3143-3159.