Single electron transfers are the fundamental atomistic events of electrochemistry. Here we describe theconstruction, properties, and behavior of a unique multifunctional architecture – the electrochemical zero-mode waveguide (E-ZMW) - capable of both optical spectroscopic and electrochemical studies of immobilized and freely diffusing redox-active single molecules. E-ZMWs are zeptoliter-volume bimodal nanoelectrochemical-nanophotonic pores each supporting two vertically separated recessed annular electrodes. They provide a link between single electron-transfer events and light emission in fluorigenic redox reactions, such as the 2e-/2H+ redox chemistry of flavin mononucleotide, FMN/FMNH2. In addition, the bimodal optical-electrochemical functionality of the E-ZMW makes it possible to perform single molecule spectroelectrochemical measurements under redox cycling conditions – both when the upper electrode is potential-controlled and using self-induced redox cycling. The ability to combine electrochemical and spectroscopic measurements at the single molecule level is a new tool for the characterization of reaction dynamics, allowing observation of phenomena down to and including single electron transfer events.

Nonclassical optics enabled imaging of single reactions

256th National Meeting (2018)

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