Surface-imprinted core-shell Au nanoparticles for selective detection of bisphenol A based on surface-enhanced Raman scattering

Surface-imprinted core-shell Au nanoparticles (AuNPs) were explored for the highly selective detection of bisphenol A (BPA) by surface-enhanced Raman scattering (SERS). A triethoxysilane-template complex (BPA-Si) was synthesized and then utilized to fabricate a molecularly imprinted polymer (MIP) layer on the AuNPs via a sol-gel process. The imprinted BPA molecules were removed by a simple thermal treatment to generated the imprint-removed material, MIP-ir-AuNPs, with the desired recognition sites that could selectively rebind the BPA molecules. The morphological and polymeric characteristics of MIP-ir-AuNPs were investigated by transmission electron microscopy and Fourier-transform infrared spectroscopy. The results demonstrated that the MIP-ir-AuNPs were fabricated with a 2nm MIP shell layer within which abundant amine groups were generated. The rebinding kinetics study showed that the MIP-ir-AuNPs could reach the equilibrium adsorption for BPA within 10min owning to the advantage of ultrathin core-shell nanostructure. Moreover, a linear relationship between SERS intensity and the concentration of BPA on the MIP-ir-AuNPs was observed in the range of 0.5-22.8mgL^-1, with a detection limit of 0.12mgL^-1 (blank±3×s.d.). When applied to SERS detection, the developed surface-imprinted core-shell MIP-ir-AuNPs could recognize BPA and prevent interference from the structural analogues such as hexafluorobisphenol A (BPAF) and diethylstilbestrol (DES). These results revealed that the proposed method displayed significant potential utility in rapid and selective detection of BPA in real samples.