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The Faraday Discussion on electrochemistry at nano-interfaces presented a platform for an incredibly diverse array of advances in electrochemical nanoscience and nanotechnology. In this summary, I have identified the factors which drive the development of the science and which ultimately support many impressive technological advances described. Prime among these are the emergence of new physical behaviors when device dimensions approach characteristic physical scaling lengths, the steadily increasing importance of surfaces as device dimensions shrink, and the capacity to fabricate and utilize structures which are commensurate in size with molecules, especially biomolecules and biomolecular complexes. In this Faraday Discussion we were treated to outstanding examples of each of these nanoscience drivers to produce new, and in many cases unexpected, electrochemical phenomena that would not be observed at larger scales. The main thrust of these collective activities has been to realize the promise implicit in several transformational experiments that were carried out in the last decades of the 20th century. Our task is not complete, and we can look forward to many additional developments springing from the same intellectual wellhead. 

Because electron transfer reactions are fundamental to life processes, such as respiration, vision, and energy catabolism, it is critically important to understand the relationship between functional states of individual redox enzymes and the macroscopically observed phenotype, which results from averaging over all copies of the same enzyme. To address this problem, we have developed a new technology, based on a bifunctional nanoelectrochemical-nanophotonic architecture - the electrochemical zero mode waveguide (E-ZMW) - that can couple biological electron transfer reactions to luminescence, making it possible to observe single electron transfer events in redox enzymes. Here we describe E-ZMW architectures capable of supporting potential-controlled redox reactions with single copies of the oxidoreductase enzyme, glutathione reductase, GR, and extend these capabilities to electron transfer events where reactive oxygen species are synthesized within the  100 zL volume of the nanopore. 

Detecting and identifying infectious agents and potential pathogens in complex environments and characterizing their mode of action is a critical need. Traditional diagnostics have targeted a single characteristic, e.g. spectral response, surface receptor, mass, intrinsic conductivity, etc. However, advances in detection technologies have identified emerging approaches in which multiple modes of action are combined to obtain enhanced performance characteristics. Particularly appealing in this regard, electrophotonic devices capable of coupling light to electron translocation have experienced rapid recent growth and offer significant advantages for diagnostics. In this chapter, we explore three specific promising approaches that combine electronics and photonics: (a) assays based on closed bipolar electrochemistry coupling electron transfer to color or fluorescence (b) sensors based on localized surface plasmon resonances, and (c) emerging nanophotonics approaches, such as those based on zero-mode waveguides and metamaterials. 

Pore-based structures occur widely in living organisms. Ion channels embedded in cell membranes, for example, provide pathways, where electron and proton transfer are coupled to the exchange of vital molecules. Learning from mother nature, a recent surge in activity has focused on artificial nanopore architectures to effect electrochemical transformations not accessible in larger structures. Here, we highlight these exciting advances. Starting with a brief overview of nanopore electrodes, including the early history and development of nanopore sensing based on nanopore-confined electrochemistry, we address the core concepts and special characteristics of nanopores in electron transfer. We describe nanopore-based electrochemical sensing and processing, discuss performance limits and challenges, and conclude with an outlook for nextgeneration nanopore electrode sensing platforms and the opportunities they present.