Toward Application of Nanodiamonds for In‐Situ Monitoring of Radicals in Liquid Phase Chemical Reactions

In many chemical reactions, short‐lived radical intermediates play a crucial role, while detecting such short‐lived species in situ remains challenging. The optically readable electronic spin of nitrogen‐vacancy (NV) centers in diamond is a nanoscale sensor for such radical species: its longitudinal spin relaxation time (T 1 ) reacts to magnetic fluctuations from the unpaired electrons of radical species in its local environment. In this setting, we demonstrate the successful in situ detection of the nitroxide radical 2,2,6,6‐Tetramethylpiperidinyloxyl (TEMPO) using NV center‐based T 1 relaxometry after depositing nanodiamonds onto the inner wall of a glass cuvette. A significant concentration‐dependent shortening of the relaxation time was observed, from 197 μs ± 21 μs without radical to 66 μs ± 30 μs at a concentration of 1 M TEMPO. At the same time, the nanodiamonds remain firmly attached to the cuvette even after the solution under investigation has been exchanged. The detection is sensitive in the nanomolar (nM) range and the determined signal‐to‐noise ratio is between 1.6 and 3.