Conventional electrochemistry and surface-enhanced Raman scattering (SERS) spectroelectrochemistry are used to probe the redox reaction of Nile Blue immobilized on gold electrodes. Covalent attachment of Nile Blue (NB) to gold through carbodiimide cross-linking shows the appearance of a second, new redox reaction, unobserved by solution phase or physisorbed NB. Each redox reaction is characterized by differential pulse voltammetry to reveal two individual one-proton, one-electron electrochemical reactions. SERS spectroelectrochemistry along with electrochemical characterization of structurally similar Cresyl Violet are used to assign the electrochemical (de)­protonation of the terminal amine and phenoxazine nitrogen to the lower and higher energy redox reactions, respectively. Analysis of covalently bound NB via azide–alkyne click chemistry supports the hypothesis that the electron-withdrawing carbonyl formed during the carbodiimide cross-linking induces a change in the electronic structure of NB, causing a shift in the terminal amine redox reaction to lower energy.

Single entity electrochemistry experiments are typically motivated by the need to reveal how heterogeneity affects performance within inherently diverse nanoparticle populations. Here we show that a commonly used supporting electrode, tin‐doped indium oxide (ITO), can also play a significant role in creating heterogeneity in nanoparticle electrochemical responses. To investigate the impact of the substrate, we optically monitored the electrodissolution kinetics of gold nanoparticles on ITO thin films with similar resistivity from two different suppliers. The ITO from the two suppliers showed marked differences in the gold electrodissolution kinetics, with ITO from one of the suppliers even producing poor sample‐to‐sample reproducibility across substrates within the same lot number. The role of nanoparticle size and surface effects were accounted for in our analysis to validate that the observed heterogeneity is dominated by the ITO electrodes. The results show that the role of the supporting electrode cannot be ignored when performing single entity structure‐function studies.

George J. Sánchez has modeled a new paradigm in his work with the almost one hundred undergraduate and graduate students he has mentored over the years. This article discusses the lessons I have learned from his scholarship and career over the years, lessons that I now share with my own students. In particular, his example challenges us to build and strengthen relationships with communities outside the academy, broaden our definitions of scholarship, and mobilize the complex power of storytelling in our research.