Colorimetric and fluorescent dual-mode strategy for sensitive detection of sulfide: Target-induced horseradish peroxidase deactivation.

Abstract

Environmental pollution caused by sulfide compounds has become a major problem for public health. Hence, accurate detection of sulfide anions (S2-) level is valuable and vital for environmental monitoring and protection. Here, we report a new colorimetric/fluorescent dual-mode sensor for the determination of S2- based on the inhibition of enzyme activity and the unique optical properties of produced 2,3-diaminophenazine (DAP), thus making the analytical results more convincing. In this strategy, horseradish peroxidase (HRP) enzyme is used for catalyzing the H2O2-mediated oxidation of o-phenylenediamine (OPD) to produce DAP, and the color changed to bright yellow and produced orange yellow fluorescence. But the presence of S2- could cause the deactivation of HRP, which decreased the amount of DAP and consequently resulted in a substantial SPR band fading and an evident fluorescence quenching simultaneously. The mechanism of S2- sensor was examined by combining the UV-vis absorption spectra, fluorescence spectra and electrospray ionization mass spectrometry analysis. Under optimal conditions, the colorimetric and fluorescent linear responses of the proposed method exhibited a wide linear range from 2.5nM-7.5μM with ultralow detection limits of 1.2nM and 0.9nM, respectively. Some potential interferents (such as F-, Cl-, Br-, I-, SO42-, SO32-, SCN-, H2PO4-, HPO42-, Ac-, NO3-, CO32-) in real samples showed no interference. Moreover, the proposed method offered advantages of simple, low-cost instruments and rapid assay without the utilization of nanomaterials and has been successfully applied to determine S2- content in lake water samples with satisfying recoveries over 97.6%. More importantly, the present S2- sensor not only afforded a new optical sensing pattern for bioanalysis and environment monitoring, but also extends the application field of HRP-catalyzed OPD-H2O2 system.