Detection of Hydrogen Peroxide and Glucose with a Novel Fluorescence Probe by the Enzymatic Reaction of Amino Functionalized MOFs Nanosheets

Amino-functionalized two-dimensional (2D) MOFs have great potential in biosensors due to their excellent water solubility, high fluorescence, large specific surface area, good adsorption properties of MOFs and good ability to enrich the target analytes. Fluorescence detection of hydrogen peroxide and glucose mostly relies on monitoring the single fluorescence intensity changes in a single excitation wavelength. Here, a ratiometric fluorescence sensor based on NH2-MIL-53(Al) nanosheets to sensitively detect H2O2 and glucose through the enzymatic reaction was developed. Meanwhile, o-phenylenediamine (OPD) was oxidized by H2O2 in the presence of horseradish peroxidase (HRP). Then, the oxidation product could be self-assembled on NH2-MIL-53(Al) nanosheets by hydrogen bonding and π-π deposition. Due to the orbital interaction or the fluorescence resonance energy transfer (FRET) between the nanosheet and the oxidation product, which could effectively quench the fluorescence of the nanosheets at 433 nm. At the same time, the oxidation product provided a new emission peak at 564 nm. The fluorescence ratio signal changes generated by this oxidation process was used to stably and sensitively detect H2O2 and glucose. The structural and mechanism analysis was carried out by the calculation methods such as AICD and ORCA to explore the π electron structure characteristic, the hole/electron orbitals and the quenching phenomenon. The detection limit was 26.9 nM for H2O2, and 0.041 μM for glucose. The detection of glucose in human serum has a satisfying recovery of 97.4%-102.8%. It is clear that the sensor has a good application prospect in real sample analysis.