Au@Ag nanodome-cones array substrate for efficient residue analysis of food samples by surface-enhanced Raman scattering

A bioinspired Au@Ag nanodome-cones array (Au@Ag NDCA) surface-enhanced Raman scattering (SERS) chip was developed for efficient residue analyses of food samples. The cicada wing inspired Au@Ag NDCA chip was fabricated by a bottom-up method, Au nanocones array was firstly grown onto nickel foil by displacement reaction and cetyltrimethylammonium bromide guidance growth, and then silver shell with controllable thickness was coated onto the Au nanocones array by magnetron sputtering. The Au@Ag NDCA chip exhibited good SERS performances with high enhancement factor of 1.2 × 108, good uniformity with relative standard deviation (RSD) less than 7.5% (n = 25), good inter-batch reproducibility with RSD less than 9.4% (n = 9), and long-term stability over 9 weeks. By adapting a minimized sample preparation, Au@Ag NDCA chip combined with a 96-well plate could realize high-throughput SERS analyses of 96 samples with average analysis time less than 10 min. The substrate was applied for quantitative analyses of two food projects. One was 6-benzylaminopurine auxin residue in sprout samples with detection limit of 38.8 μg/L, recoveries of 93.3-105.4% and RSDs of 1.5-6.5%, and the other was an edible spice of 4-amino-5,6-dimethylthieno (2,3-d) pyrimidin-2(1H)-one hydrochloride additive in beverage samples with detection limit of 18.0 μg/L, recoveries of 96.2-106.6% and RSDs of 3.5-7.9%. All the SERS results were well confirmed by conventional high-performance liquid chromatographic methods with relative errors less than 9.7%. The robust Au@Ag NDCA chip exhibited good analytical performances possessed great potential for convenient and reliable analyses of food quality and safety.