Ratiometric fluorescence assay for sulfide ions with fluorescent MOF-based nanozyme

A novel ratiometric fluorescence strategy for sulfide ions (S^2-) analysis has been developed using metal-organic framework (MOF)-based nanozyme. NH₂-Cu-MOF displays blue fluorescence (λem = 435 nm) originating from 2-amino-1,4-benzenedicarboxylic acid ligand. Besides, it possesses oxidase-like activity due to Cu²⁺ node, which can trigger chromogenic reaction. o-Phenylenediamine (OPD), as a common enzyme substrate, can be oxidized by NH₂-Cu-MOF to form luminescent products (oxOPD) (λem = 570 nm). Inner filter effect occurs between oxOPD and MOF. Upon exposure to S^2-, oxidase-like activity of MOF is depressed significantly because of the generation of CuS. On one hand, the amount of free Cu²⁺ decreases, affecting the yielding of oxOPD. On the other hand, CuNPs with larger size are obtained during the oxidation-reduction reaction between Cu²⁺ and OPD, which show weaker autocatalytic ability for OPD oxidation. These result in the decrease and increase of intensities at 570 and 435 nm, respectively. This method exhibits sensitive and selective responses towards S^2- with LOD of 0.1 μM. Furthermore, such ratiometric strategy has been applied to detect S^2- in food samples.