Phenylboronic Acid-Functionalized Ratiometric Surface-Enhanced Raman Scattering Nanoprobe for Selective Tracking of Hg2+ and CH3Hg+ in Aqueous Media and Living Cells

The development of appropriate molecular tools to monitor different mercury speciation, especially CH3Hg+, in living organisms is attractive because its persistent accumulation and toxicity are very harmful to human health. Herein, we develop a novel activity-based ratiometric SERS nanoprobe to selectively monitor Hg2+ and CH3Hg+ in aqueous media and in vivo. In this nanoprobe, a new bifunctional Raman probe bis-s-s′-[(s)-(4-(ethylcarbamoyl)phenyl)boronic acid] (b-(s)-EPBA) was synthesized and immobilized on the surface of gold nanoparticles via a Au–S bond, in which the phenylboronic acid group was employed as the recognition unit for Hg2+ and CH3Hg+ based on the Hg-promoted transmetalation reaction. In the presence of Hg2+ and CH3Hg+, a new surface-enhanced Raman scattering (SERS) peak aroused from of C–Hg appeared at 1080 cm–1, and the SERS intensity at 1002 cm–1 belonged to the B–O symmetric stretching decreased simultaneously. The quantitative tracking of Hg2+ and CH3Hg+ was realized based on the SERS intensity ratio (I1080/I1303) with rapid response (∼4 min) and high sensitivity, with detection limits of 10.05 and 25.13 nM, respectively. Moreover, the SERS sensor was used for the quantitative detection of Hg2+ and CH3Hg+ in four actual water samples with a high accuracy and excellent recovery. More importantly, cell imaging experiments showed that AuNPs@b-(s)-EPBA could quantitatively detect intracellular CH3Hg+ and had a good concentration dependence in ratiometric SERS imaging. Meanwhile, we demonstrated that AuNPs@b-(s)-EPBA could detect and image CH3Hg+ in zebrafish. We anticipate that AuNPs@b-(s)-EPBA could potentially be used to study the physiological functions related to CH3Hg+ in the future.