Surface-Enhanced Raman Scattering Optophysiology Nanofibers for the Detection of Heavy Metals in Single Breast Cancer...

Mercury(II) ions (Hg²⁺) and silver ions (Ag⁺) are two of the most hazardous pollutants causing serious damage to human health. Here, we constructed surface-enhanced Raman scattering (SERS)-active nanofibers covered with 4-mercaptopyridine (4-Mpy)-modified gold nanoparticles to detect Hg²⁺ and Ag⁺. Experimental evidence suggests that the observed spectral changes originate from the combined effect of (i) the coordination between the nitrogen on 4-Mpy and the metal ions and (ii) the 4-Mpy molecular orientation (from flatter to more perpendicular with respect to the metal surface). The relative intensity of a pair of characteristic Raman peaks (at ∼428 and ∼708 cm^-1) was used to quantify the metal ion concentration, greatly increasing the reproducibility of the measurement compared to signal-on or signal-off detection based on a single SERS peak. The detection limit of this method for Hg²⁺ is lower than that for the Ag⁺ (5 vs 100 nM), which can be explained by the stronger interaction energy between Hg²⁺ and N compared to Ag⁺ and N, as demonstrated by density functional theory calculations. The Hg²⁺ and Ag⁺ ions can be masked by adding ethylenediaminetetraacetate and Cl^-, respectively, to the Hg²⁺ and Ag⁺ samples. The good sensitivity, high reproducibility, and excellent selectivity of these nanosensors were also demonstrated. Furthermore, detection of Hg²⁺ in living breast cancer cells at the subcellular level is possible, thanks to the nanometric size of the herein described SERS nanosensors, allowing high spatial resolution and minimal cell damage.