Abuse of methenamine in foodstuff is harmful to the health of people. Routine methods recommended by the national standard are indirect assays with complicated pretreatment of samples or less sensitivity. In this work, core-shell Au nanoparticles@inositol hexaphosphate@MIL-101(Fe) nanoparticles, designated as Au@MIL-101, are successfully synthesized by layer-by-layer assembly. Metal-organic framework (MOF; MIL-101)-modified AuNPs could narrow the distance between neighboring Au@MIL-101, which increases the amount of "hot spots" and contributes excellent enhancement of Raman scattering. In addition, certain target molecules could access the proximity to the "hot spots" by the strong interaction capability of MOF with -COOH groups. Taking the syngeneic effect of "hot spots" and chemical enhancement via specific binding, Au@MIL-101-based Raman protocol with huge sensitivity is developed to achieve direct detection of methenamine. It has good linearity of dynamic concentration from 3.16 × 10 to 1.0 × 10 M with correlation coefficient ( R) of 0.9908. The limit of detection reaches 5.0 × 10 M. As a practical application, such an Au@MIL-101-based Raman protocol could be used for the direct determination of trace methenamine in vermicelli, which meets the requirements of the national standard.
In this paper, a two-step method is used to prepare a regenerative three-dimensional (3D) ZnO/Ag@Au substrate for developing a superior sensitive surface enhanced Raman scattering (SERS) method for detecting antibiotics. A great electromagnetic enhancement is observed from the as-prepared composite substrate, which is triggered by tuning the electron distribution of metals and semiconductor metal oxide. The strong interaction between target sample and the huge surface area of ZnO/Ag@Au composite promotes the charge transfer to produce promising chemical enhancement. The synergistic physical and chemical enhancement mechanisms are validated by density functional theory and finite difference time domain simulation. Additionally, the presence of light "echo effect" in the 3D structure of ZnO support could also amplify the efficiency of light excitation for Raman scattering. The above-stated merits benefit to boost the Raman scattering detection sensitivity for real samples. The ZnO/Ag@ Au-based SERS substrate could detect rhodamine 6G molecules with an enhancement factor of up to 1.48 × 10 9 and the lowest detectable concentration of 10 −10 M. As a real application, antibiotics sulfapyridine in milk is determined by using the proposed SERS protocol, and the limit of detection at 1 × 10 −9 M could be reached. As a prospective, the ZnO/Ag@Au-based SERS method would be extended for food safety and biomedicine analysis.
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