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^2+/3+ 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^-10 M to 1.0 × 10^-6 M and 1.0 × 10^-9 M to 1.0 × 10^-7 M, with detection limits of 3.9 × 10^-12 M and 1.89 × 10^-11 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.