Ag Nanoparticles@Agar Gel as a 3D Flexible and Stable SERS Substrate with Ultrahigh Sensitivity

Flexible surface-enhanced Raman scattering (SERS) substrates have become one of the research hot spots due to the facile sampling by swabbing or wrapping on rough surfaces and the sensitive and nondestructive detection of contaminants. In this work, we proposed a simple and fast in situ reduction method to prepare Ag nanoparticles (Ag NPs) composited agar hydrogel (Ag NPs@Agar) flexible SERS substrate. Owing to the three-dimensional (3D) structure, good hydrophilicity and adsorption of the agar hydrogel, Ag NPs were grown uniformly in the 3D cross-linked structure. The distribution density of Ag NPs was further increased by the volume shrinkage when the hydrogel was dried in air. This high density and uniformly distribution of Ag NPs produced a large number of highly active SERS regions. In addition, the sensitivity of Ag NPs@Agar was further improved with the assistance of hydrophilic agar gel, which can trap the probe molecules into highly active SERS areas. The SERS results showed that the substrate can be used to detect dye molecules (rhodamine 6G), the minimum detectable concentration was 10^-15 M, the relative standard deviation tested at 18 different positions was only 7.58%, and the intensity of the characteristic peak at 611 cm^-1 decreased only about 10% after 49 days of storage, demonstrating the superior stability. Moreover, the Ag NPs@Agar substrate also could successfully achieve the micro-trace detection of melamine and sodium penicillin G in Xinjiang specialty camel milk powder. The above available results show that the prepared flexible Ag NPs@Agar SERS substrates possess potentials for the illegal additives and antibiotics in food safety analysis.