Flexible paper-based Ag dendritic SERS chips for rapid in situ detection of thiram residues on pear skin†

Abstract

Surface-enhanced Raman scattering (SERS) is a powerful, highly efficient analytical technique capable of providing label-free, non-invasive, rapid, and ultrasensitive molecular detection down to the single-molecule level. Despite its advantages, SERS remains largely confined to laboratory settings due to the complexities of substrate fabrication and challenges in analyzing real-world samples. Developing flexible SERS substrates that achieve both high fabrication efficiency and high sensing performance, while being practical for field applications, is critical for advancing SERS toward broader, real-world use. In this study, we present a novel paper-based Ag dendritic SERS chip, fabricated via a simple chemical reduction process that directly forms Ag dendritic nanostructures on cellulose fibers. This chip substrate demonstrates exceptional sensitivity for the detection of thiram pesticide, with a detection limit as low as 7.76 × 10⁻¹¹ M. The chip substrate also exhibits outstanding reliability, with reproducibility and repeatability both less than 5%. Furthermore, the flexible nature of the paper substrate enables it to conform to curved surfaces and be in direct contact with analytes, exemplified by its ability to adhere to and retrieve thiram from pear skin using a novel “paste-and-peel-off” technique. The substrate shows remarkable performance for thiram detection on pear skin, with sharp recovery rates ranging from 90% to 105%. With its facile fabrication, excellent sensitivity, high reliability, and practical applicability in non-invasive sampling, the paper-based Ag dendritic SERS substrate offers significant potential as an advanced substrate to bring SERS out of the laboratory and closer to real-world applications.