by Keyword: ECSTM

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Lopez-Martinez, Montserrat, López-Ortiz, Manuel, Antinori, Maria Elena, Wientjes, Emilie, Nin-Hill, Alba, Rovira, Carme, Croce, Roberta, Díez-Pérez, Ismael, Gorostiza, Pau, (2019). Electrochemically gated long distance charge transport in photosystem I Angewandte Chemie International Edition 58, (38), 13280-13284

The transport of electrons along photosynthetic and respiratory chains involves a series of enzymatic reactions that are coupled through redox mediators, including proteins and small molecules. The use of native and synthetic redox probes is key to understand charge transport mechanisms, and to design bioelectronic sensors and solar energy conversion devices. However, redox probes have limited tunability to exchange charge at the desired electrochemical potentials (energy levels) and at different protein sites. Here, we take advantage of electrochemical scanning tunneling microscopy (ECSTM) to control the Fermi level and nanometric position of the ECSTM probe in order to study electron transport in individual photosystem I (PSI) complexes. Current-distance measurements at different potentiostatic conditions indicate that PSI supports long-distance transport that is electrochemically gated near the redox potential of P700, with current extending farther under hole injection conditions.

Keywords: Current decay, ECSTM, Electrochemical gate, Electron transfer, Photosynthesis

López-Martínez, Montserrat, Artés, Juan Manuel, Sarasso, Veronica, Carminati, Marco, Díez-Pérez, Ismael, Sanz, Fausto, Gorostiza, Pau, (2017). Differential electrochemical conductance imaging at the nanoscale Small 13, (36), 1700958

Electron transfer in proteins is essential in crucial biological processes. Although the fundamental aspects of biological electron transfer are well characterized, currently there are no experimental tools to determine the atomic-scale electronic pathways in redox proteins, and thus to fully understand their outstanding efficiency and environmental adaptability. This knowledge is also required to design and optimize biomolecular electronic devices. In order to measure the local conductance of an electrode surface immersed in an electrolyte, this study builds upon the current–potential spectroscopic capacity of electrochemical scanning tunneling microscopy, by adding an alternating current modulation technique. With this setup, spatially resolved, differential electrochemical conductance images under bipotentiostatic control are recorded. Differential electrochemical conductance imaging allows visualizing the reversible oxidation of an iron electrode in borate buffer and individual azurin proteins immobilized on atomically flat gold surfaces. In particular, this method reveals submolecular regions with high conductance within the protein. The direct observation of nanoscale conduction pathways in redox proteins and complexes enables important advances in biochemistry and bionanotechnology.

Keywords: Differential electrochemical conductance, ECSTM, Electron transport pathway, Iron passivation, Redox metalloproteins