Single-molecule studies, including those of single enzyme molecules, have led to important new insights about the effects of environment and configuration on the behavior of these molecules. Such information is not available from ensemble studies. Most of these have been based on spectroscopic approaches, but there have been relatively few attempts at single-molecule electrochemistry. In a paper in this issue, progress toward studying a single enzyme molecule by protein film voltammetry is described. This Perspective reviews briefly past work on nanoelectrodes and electrochemical and spectroelectroelectrochemical single-molecule studies, as well as examples of the type of information obtained in past studies of enzymes.
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