Paper/GO/e-Au Flexible SERS Sensors for In-situ Detection of Tricyclazole in Orange Juice and on Cucumber Skin at Sub-ppb Level: Machine Learning-Assisted Data Analysis
Abstract
Despite being an excellent surface enhance Raman scaterring (SERS) active material, gold nanoparticles were difficult to be loaded onto the surface of filter paper to fabricate flexible SERS substrates. In this study, electrochemically synthesized gold nanoparticles (e-AuNPs) were deposited on graphene oxide (GO) nanosheets in solution by ultrasonication, resulting in formation of GO/Au hybrid material. Thanks to the support of GO, the hybrid material could adhere onto the surface of filter paper, which was immersed into GO/Au solution for 24 h and dried naturally at room temperature. The paper-based materials were then employed as substrates for surface enhanced Raman scattering (SERS) sensing platform to detect tricylazole (TCZ), a widely-used pesticide, resulting in better sensitivity compared to the use of paper/Au SERS sensors. With the most optimal GO content of 4%, paper/GO/Au SERS sensors could achieve a limit of detection of 1.32 × 10-10 M in standard solutions. Furthermore, the filter paper-based SERS sensors also exhibited significant advantages in sample collecting in real samples. On one hand, the sensors were dipped into orange juice, allowing TCZ molecules in this real sample to be adsorbed onto their SERS active surface. On the other hand, they were pasted onto cucumber skin to grab the analytes. As a result, paper/GO/Au SERS sensors could sense the TCZ in orange juice and on cucumber skin at concentrations as low as 10-9 M (~ 2 ppb). In addition, a machine learning model was designed and developed, allowing the sensing system to discriminate TCZ from nine other organic compounds and predict the presence of TCZ on cucumber skin at concentrations down to 10-9 M.