Optically-Trapped Nanodiamond-Relaxometry Detection of Nanomolar Paramagnetic Spins in Aqueous Environments

Probing electrical and magnetic properties in aqueous environments remains a frontier challenge in nanoscale sensing. Our inability to do so with quantitative accuracy imposes severe limitations, for example, on our understanding of the ionic environments in a diverse array of systems, ranging from novel materials to the living cell. The Nitrogen-Vacancy (NV) center in fluorescent nanodiamonds (FNDs) has emerged as a good candidate to sense temperature, pH, and the concentration of paramagnetic species at the nanoscale, but comes with several hurdles such as particle-to-particle variation which render calibrated measurements difficult, and the challenge to tightly confine and precisely position sensors in aqueous environment. To address this, we demonstrate relaxometry with NV centers within optically-trapped FNDs. In a proof of principle experiment, we show that optically-trapped FNDs enable highly reproducible nanomolar sensitivity to the paramagnetic ion, (\mathrm{Gd}^{3+}). We capture the three distinct phases of our experimental data by devising a model analogous to nanoscale Langmuir adsorption combined with spin coherence dynamics. Our work provides a basis for routes to sense free paramagnetic ions and molecules in biologically relevant conditions.