Potential-Dependent Stochastic Amperometry of Multiferrocenylthiophenes in an Electrochemical Nanogap Transducer

Klaus Mathwig*, Hamid R. Zafarani, J. Matthäus Speck, Sahana Sarkar, Heinrich Lang, Serge G. Lemay, Liza Rassaei, Oliver G. Schmidt

*Corresponding author for this work

    Research output: Contribution to journalArticleScientificpeer-review

    9 Citations (Scopus)


    In nanofluidic electrochemical sensors based on redox cycling, zeptomole quantities of analyte molecules can be detected as redox-active molecules travel diffusively between two electrodes separated by a nanoscale gap. These sensors are employed to study the properties of multiferrocenylic compounds in nonpolar media, 2,3,4-triferrocenylthiophene and 2,5-diferrocenylthiophene, which display well-resolved electrochemically reversible one-electron transfer processes. Using stochastic analysis, we are able to determine, as a function of the oxidation states of a specific redox couple, the effective diffusion coefficient as well as the faradaic current generated per molecule, all in a straightforward experiment requiring only a mesoscopic amount of molecules in a femtoliter compartment. It was found that diffusive transport is reduced for higher oxidation states and that analytes yield very high currents per molecule of 15 fA.

    Original languageEnglish
    Pages (from-to)23262-23267
    JournalThe Journal of Physical Chemistry C
    Issue number40
    Publication statusPublished - 2016


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