Electrochemistry of complex molecular and biomolecular scale entities

Structural mapping of intermediate size and large molecules and biomolecules at ultra-high resolution using single-crystal electrodes and in situ scanning tunnelling microscopy continues to disclose surprising findings. In situ scanning tunnelling spectroscopy has also recently disclosed new electrochemical conductivity features at the level of the single molecule. We overview briefly elements of this development over the last few years, with focus on three recent discoveries: (1) a new packing mode of a core monolayer target thiol, the amino acid cysteine (Cys) on Au(100)-electrodes, quite different from Cys packing on Au(111)- and Au(110)-electrodes; (2) transition of a core ferrocene in situ scanning tunnelling spectroscopy probe from stochastic single-molecule to macroscopic behaviour, a concept at the heart of nanoscience; and (3) unexpected behaviour of the large molybdenum enzyme sulfite oxidase, when going from macroscopic to single-molecule electrochemistry. We compare these studies with other recent discoveries of single-molecule protein conductivity and molecular scale inorganic nanostructures.