Electron transfer1-7 by thermally activated hopping through localized centers is a common motif that occurs over a broad spectrum of matter such as non-conducting crystalline solids, amorphous glasses, fluidic/viscous liquids, and biomolecules. This basic kinetic motif is an essential element for a broad variety of vital biological and technological processes.8-10 New directions in electrochemistry, a discipline which has contributed greatly to developing the theoretical underpinnings of charge-transfer phenomena,1-7,11-13 promise to reveal important features of electron transfer (ET) in biomolecular redox chains. This new frontier in electrochemistry, which has been developing over the past two decades,14-53 uses chemically tunable, nanoscopic electrode structures for addressing fundamental questions in charge exchange between electrodes and biomolecules.14-21,54-88