Herein, a novel Cu/CuFe₂O₄@iron-based metal-organic framework 88 A (Cu/CuFe₂O₄@MIL-88A(Fe)) was developed through a scalable hydrothermal strategy for the magnetic dispersive solid-phase extraction of chlorpyrifos and phosalone from water, fruit juice, and vegetable samples prior to corona discharge ion mobility spectrometry analysis. The resulting nanocomposite was characterized in detail, and thus the investigation indicated that the magnetic nanocomposite had good adsorption capacity, high surface area, dispersion, and superparamagnetic properties. In addition, the fabricated sorbent provided different interactions with the target analytes, (hydrogen bonding, hydrophobic contacts, and π-π stacking interactions) resulting in the improvement of extraction efficiency. The applied method based on Cu/CuFe₂O₄@ MIL-88A(Fe) was validated by investigating the affecting parameters, including the amount of magnetic nanocomposite (10.0 mg), sample pH (7.0), salt content (7.5 % w/v), extraction time (5 min), type of elution (150 μL of methanol), and desorption time (2 min). The linearity of the method was found to be in the range of 0.6–300.0 ng mL⁻¹ and 1.5–500.0 ng mL⁻¹, for chlorpyrifos and phosalone with the coefficient of determination of ≥0.9991. The limits of detections (LODs) of 0.2 and 0.5 ng mL⁻ ¹ were obtained for the determination of chlorpyrifos and phosalone, respectively. The relative standard deviation values (RSDs %) were calculated in the range of 4.4 %–6.1 % (intra-day, n = 5) and 6.3 %–8.0 % (inter-day, n = 3) for three days. Ultimately, the developed method was successfully applied for the extraction of the desired analytes from various spiked samples with acceptable recoveries (88.3–100.4 %).

Novel porous covalent organic framework (COF) based on condensation reaction between cyanuric chloride, 4,4′-ethylendianiline, and 3,4,9,10-perylenetetracarboxylic dianhydride was synthesized via sealed tube condition. The results COF was used as a new adsorbent for solid-phase microextraction (SPME) for extracting trifluralin and chlorpyrifos from vegetables, fruit samples, and wastewater. Gas chromatograph with a corona discharge-ion mobility spectrometer as the detector was also used for analyzing the target analytes. Some parameters that affected the extraction, such as stirring rate, time and temperature of extraction and pH were investigated, exhaustively. The detection limits were 0.13, and 0.15 µg/L and the linear ranges of 0.45–20 and 0.50–25 µg/L with a linearity coefficient of 0.9965 and 0.9987 were also obtained for trifluralin and chlorpyrifos, respectively. The method was applied successfully to analyze some real samples of cucumber, carrot, grape, and agriculture wastewater, and the results showed a relative recovery in the range of 87% to 110%.

This work presents, for the first time, a fast and highly sensitive electrochemical method for determination of three organophosphorus compounds (OPs), diazinon (DZN), malathion (MLT), and chlorpyrifos (CLPF), using a modified pyrolytic graphite electrode (PGE) coupled to batch injection analysis system with multiple pulse amperometric detection (BIA–MPA). The PGE was modified by a nanocomposite based on functionalized carbon nanotubes (CNTf) and silver nanoparticles (AgNPs). The OPs samples were directly analyzed on the modified working electrode surface by BIA-MPA system in Britton-Robinson (BR) buffer 0.15 mol L⁻¹ at pH 6.0. The MPA detection of DZN, MLT and CLPF was performed using two potential pulses, which were sequentially applied on modified PGE at −1.3 V (100 ms) and +0.8 V (100 ms) for selective determination of these three OPs and working electrode cleaning, respectively. Under optimized conditions, the sensor presented a linear range of 0.1–20 μmol L⁻¹ for DZN, 1.0–30 μmol L⁻¹ for MLT and from 0.25 to 50 μmol L⁻¹ for CLPF. The limits of detection (LOD) and quantification (LOQ) of 0.35 and 1.18 μmol L⁻¹ for DZN, 0.89 and 2.98 μmol L⁻¹ for MLT, and 0.53 and 1.78 μmol L⁻¹ for CLPF were obtained. The proposed method exhibited high sensitivity of 0.068, 0.030 and 0.043 mA L μmol⁻¹ for DZN, MLT and CLPF detection, respectively. Furthermore, the BIA-MPA system provided an analytical frequency of 71 determinations per hour for direct determination of these OPs in water and food samples. The modified PGE coupled to BIA-MPA system showed a high stability of electrochemical response for OPs detection with relative standard deviation (RSD) of 1.60% (n = 20). The addition-recovery studies of the proposed method were carried out in tap water, orange juice, and apple fruit real samples, which showed suitable recovery values between 77 and 124%. The analytical performance of the developed sensor provides an attractive alternative method for OPs determination with great potential for a fast and sensitive application in contaminated samples with these pesticides.