Nanodiamond Relaxometry-Based Detection of Free-Radical Species When Produced in Chemical Reactions in Biologically Relevant Conditions.

Diamond magnetometry is a quantum sensing method involving detection of magnetic resonances with nanoscale resolution. For instance, T1 relaxation measurements, inspired by equivalent concepts in magnetic resonance imaging (MRI), provide a signal that is equivalent to T1 in conventional MRI but in a nanoscale environment. We use nanodiamonds (between 40 and 120 nm) containing ensembles of specific defects called nitrogen vacancy (NV) centers. To perform a T1 relaxation measurement, we pump the NV center in the ground state (using a laser at 532 nm) and observe how long the NV center can remain in this state. Here, we use this method to provide real-time measurements of free radicals when they are generated in a chemical reaction. Specifically, we focus on the photolysis of H2O2 as well as the so-called Haber-Weiss reaction. Both of these processes are important reactions in biological environments. Unlike other fluorescent probes, diamonds are able to determine spin noise from different species in real time. We also investigate different diamond probes and their ability to sense gadolinium spin labels. Although this study was performed in a clean environment, we take into account the effects of salts and proteins that are present in a biological environment. We conduct our experiments with nanodiamonds, which are compatible with intracellular measurements. We perform measurements between 0 and 108 nM, and we are able to reach detection limits down to the nanomolar range and typically find T1 times of a few 100 μs. This is an important step toward label-free nano-MRI signal quantification in biological environments.