We
demonstrate that fluorogenic molecules that “turn-on”
upon redox reactions can sense the corrosion of iron at the single-molecule
scale. We first observe the cathodic reduction of nonfluorescent resazurin
to fluorescent resorufin in the presence of iron in bulk solution.
The progression of corrosion is seen as a color change that is quantified
as an increase in fluorescence emission intensity. We show that the
fluorescence signal is directly related to the amount of electrons
that are available due to corrosion progression and can be used to
quantify the catalyzed increase in the rate of corrosion by NaCl.
By using modern fluorescence microscopy instrumentation we detect
real-time, single-molecule “turn-on” of resazurin by
corrosion, overcoming the previous limitations of microscopic fluorescence
corrosion detection. Analysis of the total number of individual resorufin
molecules shows heterogeneities during the progression of corrosion
that are not observed in ensemble measurements. Finally, we discuss
the potential for single-molecule kinetic and super-resolution localization
analysis of corrosion based on our findings. Single-molecule florescence
microscopy opens up a new spatiotemporal regime to study corrosion
at the molecular level.