Developing a Novel Nanoscale Porphyrinic Metal–Organic Framework: A Bifunctional Platform with Sensitive Fluorescent Detection and Elimination of Nitenpyram in Agricultural Environment

Abstract

Developing a rapid sensing platform with effective pesticide degradation capabilities integrated into a single structure and realistic application is an imminent challenge to ensure sustainable agriculture and food safety. Here, we described establishment of a bifunctional nanoscale porphyrinic metal−organic framework (MOF) probe serving as a sensor for detection of trace nitenpyram and as a photocatalyst to facilitate the pesticide degradation. Based on the signal turned "on−off", the strong fluorescence of the probe was quenched by the target, leading to the sensing range from 0.05 to 10.0 μg mL −1 and a detection limit of 0.03 μg mL −1 . Given the versatile design by which the porphyrin photosensitizers were isolated subtly in the MOF to avoid selfquenching, the probe was endowed with sustainable and efficient pesticide photodegradation activity with a degradation rate of ∼95% for nitenpyram. Our work represents powerful all-in-one MOF-derived materials jointly for sensing and degrading pesticide residues in agricultural soils and other pesticide-contaminated environments.

Nanoscale Metal-Organic Frameworks as Fluorescence Sensors for Food Safety

“…Yu et al [72] developed a 2D tetra-pyridyl calix [4]arene-decorated MOF nanosheet (MOF-Calix) for selectively sensing the glyphosate, a representative OP. Calix [4]arene on the surface of this NMOF possessed a highly accessible active site.…”

“…Figure 3. (a) the schematic energy transfer process of Tb-MOF in the presence of nitrite, reprinted with modifications from Min et al[54]; (b) the detection mechanism of the "turn off-on" sensor (Sm-MOF) for TBHQ, reprinted with modifications from Liu et al[59]; (c) Schematic diagram for synthesis of ZnPO-MOFs and their application for rapidly detecting organophosphorus pesticides, reprinted with modifications from Xu et al[64]; (d) schematic illustration for the synthesis of FMOF and its fluorescent sensing and photocatalytic applications for NIT residue, reprinted with modifications from Liu et al[66]; (e) schematic illustration showing the mechanism of EY@DUT-52 as a fluorescence sensor for pesticides, reprinted with modifications from Wei et al[71]; (f) schematic illustration for the fabrication of 2D MOF-Calix nanosheets and sensitive detection of pesticide, reprinted with modifications from Yu et al[72].…”

Advance in Methodology and Strategies To Unveil Metabolic Mechanisms of Pesticide Residues in Food Crops

“…Importantly, immunochemical methods have become increasingly popular as screening tools for the determination of non-extractable residues of pesticides or other environmental contaminants because they are fast, less expensive, and easy to carry out. , The immunochemical analysis takes advantage of the fact that antibodies (Abs) only bind to a restricted part of an antigen, the antigenic determinants, and the non-extractable residues can be presented to Abs as antigenic determinants exposed in plant tissue . Liu et al established a bifunctional nanoscale porphyrinic metal–organic framework (MOF) probe serving as a sensor for detection of trace nitenpyram and as a photocatalyst to facilitate the pesticide degradation in paddy water and soil . This excellent technique should be assessed across multiple samples from varying areas because interferences can be found as a result of the environmental conditions under which the commodities are grown or soil additives have been applied.…”

Mechanistic Insight into Charge and Energy Transfers of Luminescent Metal–Organic Frameworks Based Sensors for Toxic Chemicals

“…This was likely due to the pyridine and amine sites in nitenpyram acting as donors responsible for electrostatic interactions ( Figure a). [ 229 ] Furthermore, eosin Y (EY)‐embedded Zr(IV)‐MOFs were prepared by Wei and coworkers that exhibited RET between Zr(IV)‐MOF and EY, resulting in selective detection of pesticide nitenpyram. The roles of the nitrogen‐conjugated structure of nitenpyram and electrostatic interactions in the sensing and selective detection of 21 types of pesticide were investigated.…”

“…Reproduced with permission. [ 229 ] Copyright 2020, American Chemical Society. b) Mechanism of EY–Zr(IV)‐MOFs E@D1 and E@D3 as sensors for pesticides, and fluorescence spectra of E@D1 and E@D3 with pesticides immersed in ethanol (0.1 × 10 −3 m ).…”