Fabrication of molecularly-imprinted gold nanoparticle-embedded Fe-MOFs for highly selective SERS detection of 17β-estradiol in milk

Abstract

17β-Estradiol (17β-E2) could accumulate in humans through milk, thus causing diseases by interfering with the function of the endocrine system. However, its detection at a trace level in milk is still a challenge because of matrix interferences. In this work, a core–shell structured polydopamine molecular-imprinted gold nanoparticles (AuNP@MIP-PDA) were embedded into Fe metal–organic framework materials to form a well-defined hexagonal microspindle structure of AuNP@MIP-PDA@MIL-101(Fe). AuNP@MIP-PDA were successfully encapsulated within the MIL-101 crystals through the hydrophobic interaction between organic ligands and the aromatic groups of PDA, the chelating power of catechol groups, as well as the introduction of acetic acid. Combined with the SERS activity of AuNPs, the specific recognition sites from MIPs, and the adsorption and enrichment capability of MIL-101, the fabricated nanohybrids could be designed as highly selective SERS sensors for the detection. By effectively preventing the macromolecule adsorption and the preconcentration of 17β-E2 near the SERS-active surface, the SERS sensor could be directly applied in the selective detection of 17β-E2 in milk without tedious pretreatment. The method demonstrated an outstanding detection limit of 1.95 × 10⁻¹⁶ mol L⁻¹, without the interference mainly originating from the two analogues, estrone and estriol. These promising results foresee the potential application of this novel MIP-based SERS sensor in food and environmental sensing.