Ultrasensitive SERS Analysis of Liquid and Gaseous Putrescine and Cadaverine by a 3D-Rosettelike Nanostructure-Decorated Flexible Porous Substrate

Putrescine and cadaverine are toxic biogenic amines in spoiled food, which poses a serious threat to food security. In this work, we reported a highly sensitive three-dimensional (3D)-rosettelike surface-enhanced Raman spectroscopy (SERS) substrate functionalized with a p-mercaptobenzoic acid (p-MBA) monolayer to detect liquid and gaseous putrescine and cadaverine in pork samples. The SERS substrate was made by a combination of the merit of the 3D morphology of ZnO nanorod arrays on a flexible porous poly(vinylidene fluoride) (PVDF) membrane and the in situ chemical growth of Au nanoparticle seeds on Au film-coated ZnO nanorods, which produced a 3D-rosettelike BigAuNP/Au/ZnO/P heterostructure with abundant SERS-active hot spots that significantly enhanced the localized surface plasmonic resonance (LSPR) effect and charge-transfer (CT) effect of Raman enhancement. This SERS substrate showed high sensitivity, reproducibility, stability, and uniformity. With the p-MBA molecular monolayer as the sensing interface, our SERS substrate realized the highly sensitive and quantitative detection of liquid putrescine and cadaverine within 10 min, with a limit of detection (LOD) of 3.2 × 10^-16 and 1.6 × 10^-13 M, respectively. Additionally, the sensor showed efficient SERS responses to gaseous amine molecules at low concentrations (putrescine: 1.26 × 10^-9 M, cadaverine: 2.5 × 10^-9 M). Further, the sensor was successfully applied to determine the total content of putrescine and cadaverine. Moreover, the practicability of this SERS sensor was verified by the measurement of liquid and gaseous amines in pork samples, and it showed great potential applications for sensitive detection of food spoilage.