Low-cost signal enhanced colorimetric and SERS dual-mode paper sensor for rapid and ultrasensitive screening of mercury ions in tea.

Mercury ions (Hg) are highly toxic heavy metals that are commonly found in natural environments. Owning to their non-biodegradability and accumulation in the food chain, the precise detection of trace amounts of Hg is essential for preventing chronic accumulation and ensuring food safety. In this study, we present a dual-mode paper sensor for simultaneous colorimetric and Surface-Enhanced Raman Spectroscopy (SERS) detection of Hg in tea, achieving ultrasensitive, rapid, and on-site screening. 4-Mercaptopyridine (4-MPY) was effectively chemisorbed onto the gold nanoparticles (AuNPs), acting as a signal probe for colorimetric methods. Moreover, it can produce plasmonic hot spots for SERS by interacting with the pyridine ring. To enhance the signal intensity of both colorimetry and SERS, a silver shell is in-situ grown on the surface of AuNPs captured on the paper sensor by reduction of Ag, achieving signal amplification. The visual limit of detection (LOD) for the colorimetric biosensor is 2.5 pM, while the LOD of SERS is 0.48 pM with this dual-mode paper sensor. The sensitivity of both the colorimetric method and SERS was improved by approximately 200 and 500 times, respectively, with the designed signal amplification strategy. The system allows for multiple parallel screening of the same sample, ensuring accurate results without any false-positive or false-negative. This study provides a valuable platform for the accurate detection of various other heavy metal ions and provides effective strategies for improving the performance of colorimetric methods.