Facile synthesis of dual-hydrolase encapsulated magnetic ZIF-8 composite for efficient removal of multi-pesticides induced pollution in water.

Multi-pesticides pollution induced by organophosphorus insecticides (OPs) and aryloxyphenoxypropionate herbicides (AOPPs) has become a significant challenge in bioremediation of water pollution due to their prolonged and over application. Though a number of physical, chemical, and biological approaches have been developed for different pesticides, the explorations usually focus on eliminating single pesticide pollution. Herein, a heterostructure nanocomposite OPH/QpeH@mZIF-8, encapsulating OPs hydrolase OPH and AOPPs hydrolase QpeH in the magnetic zeolitic imidazolate frameworks-8 (mZIF-8), was synthesized through a facile one-pot method in aqueous solution. The immobilized OPH and QpeH in mZIF-8 showed high activities towards the two most common OPs and AOPPs, i.e., chlorpyrifos and quizalofop-P-ethyl, which were hydrolyzed to 3,5,6-Trichloro-2-pyridino (TCP) and quizalofop acid, respectively. Moreover, the magnetic nanocatalyst possessed great tolerance towards broad pH range, high temperatures, and different chemical solvents and excellent recyclability. More importantly, compared to free OPH and QpeH, OPH/QpeH@mZIF-8, with significantly enhanced degradation capability, exhibited enormous potential for simultaneous removal of chlorpyrifos and quizalofop-p-ethyl from the surface and industrial wastewater. Overall, the study demonstrates the applicability of this strategy for utilizing magnetic nanocatalysts encapsulating multiple enzymes due to its simplicity, high efficiency, and economic benefits to removing pesticide compound pollution from various water resources.

Magnetic ZIF-8-Based Mimic Multi-enzyme System as a Colorimetric Biosensor for Detection of Aryloxyphenoxypropionate Herbicides.

In the present study, a magnetic mimic multi-enzyme system was developed by encapsulating the aryloxyphenoxypropionate (AOPP) herbicide hydrolase QpeH and alcohol oxidase (AOx) in zeolitic imidazolate framework (ZIF-8) nanocrystals with magnetic Fe3O4 nanoparticles (MNPs) to detect AOPP herbicides. The structural, protein loading capacity and loading ratio, porosity, and magnetic properties of QpeH/AOx@mZIF-8 were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen sorption, and vibrating sample magnetometry. An AOPP herbicide colorimetric biosensor made with QpeH/AOx@mZIF-8 had the highest sensitivity toward quizalofop-P-ethyl (QpE) with a limit of detection of 8.2 µM. This system was suitable to detect two other AOPP herbicides, including fenoxaprop-P-ethyl (FpE) and haloxyfop-P-methyl (HpE). The practical application of the biosensor was verified through quantitative analysis of QpE residues in industrial wastewater and field soils. Furthermore, QpeH/AOx@mZIF-8 exhibited excellent long-term storage stability (at least 50 days), easy separation by magnet, and reusability (at least 10 cycles), supporting its promising role in simple and low-cost detection of AOPP herbicides in real environmental samples.

Fabrication and characterization of purified esterase-embedded zeolitic imidazolate frameworks for the removal and remediation of herbicide pollution from soil.

The fragility and high cost of enzymes represent critical challenges limiting their practical application in the removal of pesticides. Herein, an aryloxyphenoxypropionate herbicide-hydrolyzing enzyme, QpeH, was purified via one-step affinity chromatography and embedded into two types of zeolitic imidazolate frameworks (ZIFs) through biomimetic mineralization. The catalytic activity towards the herbicide quizalofop-P-ethyl, the loading capacity and efficiency of the resulting two composites, QpeH@ZIF-10 with cruciate flower-like morphology and QpeH@ZIF-8 with rhombic dodecahedral morphology, were compared. Both composites had excellent stability and reusability after 10 reuse cycles, with QpeH@ZIF-10 having a better performance. More importantly, when applied for the removal of quizalofop-P-ethyl pollution in the watermelon field, QpeH@ZIF-10 (88%) showed a remarkably improved degradation efficiency compared to QpeH@ZIF-8 (84%) despite the latter having a greater loading capacity. Finally, the use of QpeH@ZIF composites was shown to recover the bacterial community in soil. This work provides a new insight into the low-cost synthesis of nanobiocatalysts combining simple purified enzymes and metal-organic frameworks (MOFs) for the remediation of pesticide-contaminated soils.