Ratiometrically electrochemical and colorimetric dual-mode detection of glyphosate based on 2D Cu-TCPP(Fe) NSs.

In this work, a dual-signal output sensor was developed for the ratiometrically electrochemical and colorimetric detection of glyphosate (GLYP) based on the duplex nature of 2D Cu-TCPP(Fe) nanosheets (2D Cu-TCPP(Fe) NSs). Cu active center sites in 2D Cu-TCPP(Fe) NSs could transform into CuCl for signal amplification in the presence of chloride ions (Cl), which dropped dramatically upon GLPY addition due to the strong interaction between GLYP and cuprous ion triggering the competitive reaction with the conversion of CuCl into Cu-GLYP complex. Meanwhile, the constant current signals of Fe in the iron-porphyrin structure of Cu-TCPP(Fe) served as an inner reference, resulting in a ratiometrically electrochemical GLYP sensor. Moreover, 2D Cu-TCPP(Fe) NSs with intrinsic peroxidase-like activity was employed for the colorimetric determination of GLYP based on the specific inhibitory effect of GLYP on the peroxidase activity of 2D Cu-TCPP(Fe) nanozyme. GLYP concentrations can be quantified in the range from 1.0 × 10 M to 1.0 × 10 M and 1.0 × 10 M to 1.0 × 10 M, with detection limits of 3.9 × 10 M and 1.89 × 10 M for ratiometrically electrochemical method and colorimetric assay, respectively. Such a dual-mode sensor with remarkable selectivity, reproducibility, and stability was finally applied for GLYP detection in real samples and reliable outcomes were achieved.