Mechanistic investigation and dual-mode colorimetric-chemiluminescent detection of glyphosate based on the specific inhibition of Fe3O4@Cu nanozyme peroxidase-like activity

In this study, a dual-mode colorimetric/CL nanosensor was developed for glyphosate detection based on the specific inhibition of Fe3O4@Cu peroxidase-like activity. Synthesized Fe3O4@Cu exhibited high levels of peroxidase-like activity that triggered the oxidation of luminol/3,3 ',5,5 '-tetramethyl benzidine dihydrochloride (TMB) to excited-state 3-aminophthalic acid/blue oxTMB, thereby delivering a CL signal/visible colorimetric signal, however, the presence of glyphosate inhibited this activity, resulting in a decrease in signal strength. Indepth investigation revealed that this inhibitory mechanism occurs via two pathways: one in which glyphosate chelates with Fe(III)/Cu(II) and occupy the catalytical active sites of Fe3O4@Cu, thereby decreasing the generation of center dot OH, and another in which glyphosate competes with TMB to consume generated center dot OH, thus reducing the oxidation of TMB. This mechanism formed the basis of our novel dual-mode colorimetric/CL glyphosate nanosensor, which achieved limits of detection (LODs) of 0.086 mu g/mL and 0.019 mu g/mL in tests, thus demonstrating its significant potential for on-site glyphosate monitoring.