Highly selective colorimetric determination of glutathione based on sandwich-structured nanoenzymes composed of gold nanoparticle–coated molecular imprinted metal–organic frameworks

A sandwich-structured composite nanoenzyme (NH₂-MIL-101(Fe)@Au@MIP) was prepared using molecularly imprinted polymers, metal–organic frameworks, and gold nanoparticles and a highly selective glutathione (GSH) colorimetric sensor was constructed. The inner part of the composite nanoenzymes is a metal–organic framework loaded with gold nanoparticles (AuNPs), NH₂-MIL-101(Fe)@Au, which has superior peroxidase-like activity compared with  NH₂-MIL-101(Fe). This is due to the surface plasmon resonance effect of AuNPs. GSH can form strong Au–S bonds with AuNPs, which can significantly reduce the enzymatic activity of NH₂-MIL-101(Fe)@Au, thereby changing the absorbance at 450 nm of the sensing system. The degree of change in absorbance is correlated with the concentration of GSH. In the outer part, the molecularly imprinted polymer with oxidized glutathione (GSSG) as a dummy template provided specific pores, which significantly improved the selectivity of the sensing system. The sensor showed good GSH sensing performance in the range 1 ~ 50 μM with a lower limit of detection (LOD) of 0.231 μM and good sensing performance in fetal bovine serum, indicating its high potential for clinical diagnostic applications.