Direct and Specific Detection of Glyphosate Using a Phosphatase-like Nanozyme-Mediated Chemiluminescence Strategy

Most organophosphorus pesticide (OP) sensors reported in the literature rely on the inhibition effect of OPs on the activity of acetylcholinesterase (AChE), which suffer from the drawbacks of lack of selective recognition of OPs, high cost, and poor stability. Herein, we proposed a novel chemiluminescence (CL) strategy for the direct detection of glyphosate (an organophosphorus herbicide) with high sensitivity and specificity, which is based on the porous hydroxy zirconium oxide nanozyme (ZrO_X-OH) obtained via a facile alkali solution treatment of UIO-66. ZrO_X-OH displayed excellent phosphatase-like activity, which could catalyze the dephosphorylation of 3-(2'-spiroadamantyl)-4-methoxy-4-(3'-phosphoryloxyphenyl)-1,2-dioxetane (AMPPD) to generate strong CL. The experimental results showed that the phosphatase-like activity of ZrO_X-OH is closely related to the content of hydroxyl groups on their surface. Interestingly, ZrO_X-OH with phosphatase-like properties exhibited a unique response to glyphosate because of the consumption of the surface hydroxyl group by the unique carboxyl group of glyphosates and was thus employed to develop a CL sensor for direct and selective detection of glyphosate without using bio-enzymes. The recovery for glyphosate detection of cabbage juice ranged from 96.8 to 103.0%. We believe that the as-proposed CL sensor based on ZrO_X-OH with phosphatase-like properties supplies a simpler and more highly selective approach for OP assay and provides a new method for the development of CL sensors for the direct analysis of OPs in real samples.