A ratiometric fluorescence sensor for detection of organophosphorus pesticides based on enzyme-regulated multifunctional Fe-based metal-organic framework.

The residues of organophosphorus pesticides (OPs) are increasing environmental pollution and public health concerns. Thus, the development of simple, convenient and sensitive method for detection of OPs is crucial. Herein, a multifunctional Fe-based MOF with fluorescence, catalytic and adsorption, is synthesized by a simple one-pot hydrothermal method. The ratiometric fluorescence sensor for detection of OPs is constructed by using only one multifunctional sensing material. The NH2-MIL-101(Fe) is able catalyze the o-phenylenediamine (OPD) into 2,3-diaminophenazine (DAP) in the presence of H2O2. The generated DAP can significantly quench the intrinsic fluorescence of NH2-MIL-101(Fe) by the fluorescence resonance energy transfer (FRET) and internal filtration effect (IFE), while producing a new measurable fluorescence. Without immobilization or molecular imprinting, pyrophosphate ion (PPi) can inhibit the peroxidase-like activity of the NH2-MIL-101(Fe) by chelating with Fe3+/Fe2+ redox couple. Moreover, PPi can also be hydrolyzed by alkaline phosphatase (ALP), the presence of OPs inhibits the activity of ALP, resulting in the increase of extra PPi preservation and signal changes of ratiometric fluorescence, the interactions of ALP with different OPs are explored by molecular docking, the OPs (e.g., glyphosate) interact with crucial amino acid residues (Asp, Ser, Ala, Lys and Arg) are indicated. The proposed sensor exhibits excellent detection performance for OPs with the detection limit of 18.7 nM, which provides a promising strategy for detection of OPs.

Microwave-assisted esterification and electro-enhanced solid-phase microextraction of omega-3 polyunsaturated fatty acids in eggs.

Omega-3 polyunsaturated fatty acids (ω-3 PUFAs), a type of fatty acid that has many health benefits, are of increasing concern. Herein, we developed a method for the rapid esterification and enrichment of ω-3 PUFAs in eggs, which includes microwave-assisted esterification (MAE) and electrically enhanced solid-phase microextraction (EE-SPME). Combined with gas chromatographic, efficient detection of ω-3 PUFAs was achieved in eggs. Under microwave radiation, the esterification efficiency exhibited a significant increase ranging from 5.06 to 10.65 times. The EE-SPME method reduced extraction time from 50 to 15 min. In addition, improvements in extractive fiber coating materials were explored, which ensured efficient extraction of ω-3 PUFAs. Under the optimal conditions, the method displayed a low detection limit (1.01-1.54 µg L-1), good recoveries (85.82%-106.01%), and wide linear range (7.5-1000 µg L-1), which was successfully applied to determine ω-3 PUFAs in real egg samples.

Highly efficient heterogeneous electro-Fenton reaction for tetracycline degradation by Fe-Ni LDH@ZIF-67 modified carbon cloth cathode: Mechanism and toxicity assessment.

In this work, a novel and efficient Fe-Ni LDH@ZIF-67 catalyst modified carbon cloth (CC) cathode was developed for tetracycline (TC) degradation in heterogeneous electro-Fenton (Hetero-EF) process. Compared to Fe-Ni LDH/CC (75.7%), TC degradation rate of Fe-Ni LDH@ZIF-67/CC cathode increased to 95.6% within 60 min. The synergistic effect of hetero-EF and anodic oxidation process accelerated electron transfer, the maximum H2O2 production of Fe-Ni LDH@ZIF-67/CC electrode reached 264 mg/L, improving utilization efficiency of H2O2. The cathode possessing a satisfied TC degradation performance over a wide pH (3-9). Free radical capture experiment revealed the collaboration of ·O2-, ·OH, and 1O2 play a significant role in TC degradation. The 5 cycles experiment and metal ion leaching experiment showed that the proposed Fe-Ni LDH@ZIF-67/CC has good recyclability and stability. In addition, the proposed Fe-Ni LDH@ZIF-67/CC cathode achieved satisfying performance in real water (tap water: 97.3%, lake water: 97.7%), demonstrating the possibility for practical application. TC degradation pathways were proposed by theory analysis and experimental results. The toxicity of TC intermediates was reduced by Hetero-EF degradation according to Toxicity Estimation Software Tool and Escherichia coli growth inhibition experiments. This work provides a novel modified cathode to improve removal efficiency of antibiotics in wastewater.

Covalent organic framework reinforced hollow fiber bar for extraction and detection of bisphenols from beverages.

Bisphenols (BPs) can migrate from packaging materials into foods, resulting in potentially harmful residues. For example, accumulation of BPs is associated with endocrine disorders. Owing to matrix effects, development of an effective and eco-friendly sample pretreatment would be helpful for BPs detection in beverages packed in plastic containers. In this work, an extraction bar, composed of hollow fiber (HF) functionalized with covalent organic frameworks (COF@Tp-NDA) and 1-ocanol, was prepared for extraction of five BPs simultaneously. The synergistic effect of COF@Tp-NDA and 1-octanol improved the extraction efficiency of BPs from milk-based beverage, juice, and tea beverage. Under optimal conditions, limits of detection ranged from 0.10 to 2.00 ng mL-1 (R2 ≥ 0.9974) and recoveries ranged from 70.1 % to 106.8 %. This method has the potential to enrich BPs, supporting their accurate determination in complex beverages.

Covalent organic framework-sodium alginate-Ca2+-polyacrylic acid composite beads for convenient dispersive solid-phase extraction of neonicotinoid insecticides in fruit and vegetables.

Neonicotinoids, the fastest-growing class of insecticides, have posed a multi-media residue problem with adverse effects on environment, biodiversity and human health. Herein, covalent organic framework-sodium alginate-Ca2+-polyacrylic acid composite beads (CACPs), facilely prepared at room temperature, were used in convenient dispersive solid-phase extraction (dSPE) and combined with high-performance liquid chromatography (HPLC) for the detection of five neonicotinoid insecticides (thiamethoxam, acetamiprid, dinotefuran, clothianidin, imidacloprid). CACPs can be completely separated within 1 min without centrifugation. After seven adsorption/desorption cycles, it maintained high extraction efficiencies (>90%). The developed method exhibited a wide linear range (0.01 âˆ¼ 10 µg mL-1), low limits of detection (LODs, 0.0028 âˆ¼ 0.0031 mg kg-1), and good repeatability (RSD ≤ 8.11%, n = 3). Moreover, it was applied to the determination of five neonicotinoids in fruit and vegetables (peach, pear, lettuce, cucumber, tomato), and recoveries ranged from 73.6% to 116.2%.

Membrane-protected magnetic covalent organic framework for efficient extraction of estrogens in dairy products.

The presence of estrogens residues in dairy products is a growing concern due to their potential health risk. Herein, in this study, we have developed a membrane-protected magnetic solid-phase extraction (MP-MSPE) method that utilized a magnetic adsorbent (Fe3O4@COF-LZU1) with in-situ growth for the efficient extraction of estrone (E1), 17ß-estradiol (E2), and estriol (E3). When combined with HPLC-FLD, this method allows for the efficient detection of estrogens in dairy products. The stability of the MP-MSPE was improved by the presence of a dialysis membrane, which remained a high extraction efficiency (90 %) even after ten reuse cycles. The hydrogen bonding, π-π interactions and pore size effect contribute to the excellent adsorption of three estrogens onto Fe3O4@COF-LZU1. Under optimal conditions, the method exhibits a low detection limit (0.01-0.15 µg L-1), wide linear range (0.1-800 µg L-1), and favorable recoveries (77.3 %-109.4 %) at three concentration levels (10, 50 and 100 µg L-1). This proposed method is characterized by its simplicity, high efficiency and eco-friendliness, making it a promising approach for extracting estrogens from dairy products.

Metal-organic frameworks modified melamine foam in pipette-tip for rapid solid-phase extraction of organophosphorus pesticides in fruits and vegetables.

In this work, metal-organic frameworks (MOFs) including Fe-MIL-101 and Ti-MIL-125 were prepared and fixed on the melamine foam (MF) by polyvinylidene fluoride (PVDF) to prepare MF/PVDF/MOFs, which was used as adsorbents in pipette-tip solid-phase extraction (PT-SPE) for rapid extraction of organophosphorus pesticides (OPPs). Then, a gas chromatograph-flame thermionic detector (GC-FTD) was used for simultaneous analysis of Dimethoate (DMT), Iprobenfos (IBF), Parathion-methyl (PAM), and Chlorpyrifos (CPF). The morphology, crystal structure, and functional groups of MF/PVDF/MOFs were characterized, indicating that Ti-MIL-125 and Fe-MIL-101 were successfully synthesized and distributed on MF. The Fe-MIL-101 and Ti-MIL-125 showed good extraction ability for OPPs, which was mainly due to the π-π interaction and the multiple porous structures. Under the optimal conditions, the limit of detection (LODs) of four OPPs was 0.03-0.14 µg L-1 and the RSDs were less than 9.9%. The developed PT-SPE method showed a short extraction time (<3 min). The recoveries in fruits and vegetables (Celery, cabbages, and oranges) ranged from 75.3%-118.8% (RSDs<9.6%). The prepared MF/PVDF/MOFs demonstrated the efficient extraction performance of OPPs, contributing to the rapid pretreatment of OPPs from food and the environment.

Electrochemical oxidation diminished toxicity of zearalenone significantly, while reduction increased.

Zearalenone (ZEN), one of the most common mycotoxins in cereals, poses a severe health risk to humans. In this study, electrochemical oxidation and reduction degraded ZEN in solution completely within 8 min and 20 min. The structure of ZEN products was elucidated by mass spectrometry (MS), and their toxicity was evaluated by ECOSAR software and cytotoxicity assay. From simulation, electrochemical oxidation products had lower acute and chronic toxicity, and the product at 9.0 V is not harmful (LC50/EC50 greater than 100 mg/L, ChV greater than 10 mg/L). CCK-8 assay further confirmed their less cytotoxicity. To our surprise, LC50, EC50, and ChVs of all electrochemical reduction products were lower than 1 mg/L, and cell viabilities were less than ZEN, meaning the higher toxicity of electrochemical reduction products. On this Basis, electrochemical oxidation was applied in ZEN contaminated wheat with a degradation rate of 92.32 ± 2.37%, indicating its potential to degrade ZEN practically.

Fabrication of ß-cyclodextrin-polyacrylamide/covalent organic framework hydrogel at room temperature for the efficient removal of triazole fungicides from environmental water.

Triazole is frequently-used fungicide, which can leach into surface water through farmland and cause serious environmental pollution. Continuous exposure to triazole fungicides may cause harm to human health. Herein, ß-cyclodextrin-polyacrylamide/covalent organic framework (ß-CD-PAAM/TFPB-BD) hydrogel was fabricated at room temperature and used for the efficient removal of triazole fungicides. It displayed a short adsorption equilibrium time (50 min) and a total qe of 79.92 mg g-1. The adsorption process for triazole fungicides on ß-CD-PAAM/TFPB-BD hydrogel conforms to the pseudo-second-order kinetic model and Freundlich model. The prepared hydrogel was recyclable and resistant to salt, high temperature, acid, and alkali. The reusability of fabricated sorbent can be achieved (i.e., five extraction cycles) for removal of target fungicides. Moreover, the ß-CD-PAAM/TFPB-BD hydrogel was successfully applied to remove triazole fungicides in environmental water with removal efficiency ranging from 79.4% to 99.0%.

Ratio fluorescence test strip visualized by amino-functionalized metal-organic framework for rapid sensing of glyphosate.

As glyphosate is a broad-spectrum herbicide extensively used in agriculture worldwide, rapid glyphosate detection is essential for food safety and human health. Herein, a ratio fluorescence test strip was prepared and coupled with an amino-functionalized bismuth-based metal-organic framework (NH2-Bi-MOF) that bonded with copper ion for rapid visualization and determination of glyphosate. NH2-Bi-MOF had excellent fluorescence performance, and the copper ion, a Lewis acid, was selected as the quencher. The strong chelation of glyphosate with copper ion and its quick interaction with NH2-Bi-MOF would turn on the fluorescence signal, thus enabling the quantitative sensing of glyphosate, with a linear range of 0.10-200 µmol L-1, and recoveries between 94.8% and 113.5%. The system was then expanded to a ratio fluorescence test strip, in which the fluorescent ring sticker was set as a binding-in self-calibration to reduce errors from the angle and light dependency. The method realized the visual semi-quantitation referring to a standard card, as well as the ratio quantitation using the gray value output with LOD of 0.82 µmol L-1. And the as-developed test strip was accessible, portable, and reliable, thus offering a platform for the rapid on-site detection of glyphosate and other residual pesticides.

Bismuth-based metal-organic framework peroxidase-mimic nanozyme: Preparation and mechanism for colorimetric-converted ultra-trace electrochemical sensing of chromium ion.

A colorimetric-electrochemical dual-mode analytical method based on bismuth metal-organic framework nanozyme was developed for label-free and trace/ultra-trace Cr6+ detection. 3D ball-flower shaped bismuth oxide formate (BiOCOOH) was used as the precursor and template to facilely construct the metal-organic framework nanozyme BiO-BDC-NH2, which possesses intrinsic peroxidase-mimic activity to effectively catalyze the colorless 3,3',5,5'-tetramethylbenzidine into blue oxidation products in the presence of hydrogen peroxide. Based on Cr6+ to promote the peroxide-mimic activity of BiO-BDC-NH2 nanozyme, a colorimetric method for Cr6+ detection was developed with the detection limit of 0.44 ng mL-1. Cr6+ can be electrochemically reduced to Cr3+ that would specifically inhibit the peroxidase-mimic activity of BiO-BDC-NH2 nanozyme. Thus, the colorimetric system for Cr6+ detection was converted into a low-toxic and signal-off electrochemical sensor. The electrochemical model showed upgraded sensitivity and a lower detection limit of 9.00 pg mL-1. The dual-model method was developed for selective appropriate sensing instruments in different detection scenarios, which can provide built-in correction for environmental effects, as well as the development and utilization of dual-signal sensing platforms for trace to ultra-trace Cr6+ rapid assay.

Paper-based analytical device coupled with Bi-MOF: Electric field amplification and fluorescence sensing of glyphosate.

Glyphosate, a potent herbicide wildly used in the world, involves potential hazards to human health by accumulating in the food chain. Due to its absence of chromophores and fluorophores, the rapid visual detection of glyphosate has always been difficult. Herein, a paper-based geometric field amplification device visualized by the amino-functionalized bismuth-based metal-organic framework (NH2-Bi-MOF) was constructed for sensitive fluorescence determination of glyphosate. Fluorescence of the synthesized NH2-Bi-MOF was immediately enhanced by interaction with glyphosate. The field amplification of glyphosate was implemented by coordinating the electric field and the electroosmotic flow, which was orchestrated by the geometric configuration of paper channel and the concentration of polyvinyl pyrrolidone, respectively. Under the optimal conditions, the developed method exhibited a linear range of 0.80-200 µmol L-1 with about 12500-fold signal enhancement achieved by just 100 s electric field amplification. It was applied to soil and water with recoveries between 95.7% and 105.6%, holding great prospects in on-site analysis of hazardous anions for environment safety.

Magnetic covalent organic frameworks for rapid solid-phase extraction of phthalate esters and bisphenol A in beverage samples.

Phthalate esters (PAEs) and bisphenol A (BPA) are endocrine-disrupting chemicals (EDCs), which are widely used in the production of food plastic packaging and easily migrate to food. Continuous exposure to EDCs may cause harm to human health. Herein, magnetic covalent organic framework TFP-NDA/Fe3O4 was synthesized by magnetizing covalent organic framework TFP-NDA through a facile coprecipitation method, and used as an adsorbent for rapid solid-phase extraction of PAEs (diethyl phthalate (DEP), diisobutyl phthalate (DIBP) and dibutyl phthalate (DBP)) and BPA. The extraction equilibrium can be reached within 12 min. By combination with a gas chromatography-flame ionization detector, the limits of detection were 0.7-2.3 µg L-1 and the linear ranges were 10-500 µg L-1 for diethyl phthalate (DEP) and 10-1000 µg L-1 for diisobutyl phthalate (DIBP), dibutyl phthalate (DBP) and BPA with R2 > 0.9916. In beverage samples (plastic bottled drinking water, juice and carbonated drink), the developed method was successfully applied to extract and quantify PAEs and BPA with recoveries ranging from 81.7% to 114.2%.

A stack-up electrochemical device based on metal-organic framework modified carbon paper for ultra-trace lead and cadmium ions detection.

A portable device is conducive to the on-site detection of heavy metal ions at trace level in food and the prevention of related food safety issues. In this work, an electrochemical device stacked up with flat electrodes was developed for the detection of Pb2+ and Cd2+. The top layer of the device is a carbon paper as working electrode, which is modified with amino functionalized cobalt-based metal-organic framework and gold nanoparticles. The bottom layer was constructed with the carbon counter electrode and Ag/AgCl reference electrode, and a punched sample cell (Φ = 8 mm) was in the middle. The proposed method could simultaneously determinate Pb2+ and Cd2+ via anodic stripping voltammetry with the detection limit of 7.0 × 10-2 ng mL-1 and 1.1 × 10-2 ng mL-1, and was applied in real food samples (drinking water, juice, tea, grain, fruits, vegetables, liver and aquatic products) with the recovery of 91.2-105.4 % and 90.2-111.2 %, respectively.

Covalent organic framework in situ grown on Fe3O4 hollow microspheres for stir bar sorptive-dispersive microextraction of triazole pesticides.

Based on covalent organic framework (COF) 1,3,5-tris-(4-formylphenyl)benzene-benzidine (TFPB-BD) in situ grown on Fe3O4 hollow microspheres and combined with gas chromatography-flame thermionic detector, a rapid and simple stir bar sorptive-dispersive microextraction method was developed for the determination of five triazole pesticides (paclobutrazol, hexaconazole, flusilazole, propiconazole, and tebuconazole). The synthesized TFPB-BD/Fe3O4 microspheres were characterized by transmission electron microscope, vibrating sample magnetometer, and thermogravimetric analysis, which showed that the material has strong magnetism and higher load capacity of COF. Under optimal conditions, the extraction equilibrium could be achieved within 9 min with detection limits of 0.17-1.48 µg L-1 (S/N = 3) and a linear range of 5-1000 µg L-1. The developed method was applied to the determination of trace triazole pesticides in apples, pears, and cabbages with recoveries from 81 to 117%.

Electro-enhanced solid-phase microextraction with membrane protection for enrichment of bisphenols in canned meat.

Bisphenols (BPs), one of the endocrine disrupting chemicals (EDCs), are harmful to health with the potential carcinogenicity, teratogenicity and neurotoxicity. In this paper, we developed an electro-enhanced solid-phase microextraction with membrane protection method to enrich BPs. The extraction time can be shortened to 10 min with the electric field, and the prepared fiber can be repetitively used 100 times with the membrane protection. The factors affecting extraction such potential, pH, extraction temperature and extraction time were optimized. Under optimal conditions, the linear ranges were 2-600 ng mL-1 for BPAF and 2-800 ng mL-1 for the other four BPs (BPB, BPF, BPA, BPZ), and the limits of detection (S/N=3) were from 0.09 (BPAF) to 0.41 (BPA) ng mL-1, with intra-day and inter-day precisions <5.16% and 9.29%, respectively. The developed method has been applied to the determination of trace BPs in canned meat with the recoveries of 73%-117%, showing a promising application for pretreatment in complex samples.

A ratio fluorescence sensor based on rhodamine B embedded metal-organic framework for glyphosate detection in agri-food products.

Glyphosate, a broad-spectrum and high-efficiency herbicide, could accumulate in the human body through the consumption of agri-food products. Herein, a ratio fluorescence sensor based on rhodamine B-embedded amino-functionalized iron-based metal-organic framework (MOF, NH2-MIL-88(Fe)@RhB) bonded with Cu2+ was developed for rapid detection of glyphosate. The synthesized NH2-MIL-88(Fe) was a biconical prism and had a cavity for the embedding of RhB as a reference compound. In the presence of Cu2+, Lewis interactions with NH2-MIL-88(Fe)@RhB cause the fluorescence signal to be turned off. When glyphosate was added, the signal was turned on due to chelation with Cu2+ and hydrogen bonding interactions with NH2-MIL-88(Fe)@RhB. Under optimal conditions, the developed sensor exhibited a linear range of 0.60-45 µmol L-1 with a response time of less than 1 min. The sensor was applied in the analysis of agri-food products (tea, soybean, wheat, cucumber), with recoveries between 97.93% and 109.06%, indicating its promising application in agri-food safety.

Metal-organic framework modified carbon cloth for electric field enhanced thin film microextraction of sulfonamides in animal-derived food.

Sulfonamides (SAs) were widespread in animal-derived food at trace level, which could trigger hazards to human health. Herein, electric field enhanced thin-film microextraction (EE-TFME) was developed based on carbon cloth (CC) modified with metal-organic frameworks (MOFs) for extraction of SAs (sulfadiazine, sulfathiazole, sulfamerazine, sulfadimidine, sulfamethoxazole and sulfisoxazole), which were a series of polar analytes. MIL-101(Cr) was in situ synthesized on CC via hydrothermal reaction and then was used as positive electrode in EE-TFME for adsorption of SAs. Compared with traditional TFME, EE-TFME shortened extraction equilibrium time from 30 min to 15 min. Coupled with high-performance liquid chromatography (HPLC), the limits of detection (LODs) were 2.5-4.5 µg/L, while the repeatability and intermediate precision was lower than 9.1%. Quantitative determination of SAs in extracts of animal-derived samples, such as honey, pork, chicken and milk, was achieved with recoveries from 81.7% to 114.2%. The developed MOF/CC-based EE-TFME has a great potential in rapid extraction of similar polar or ionic analytes from complex food matrices.

Covalent organic framework modified carbon cloth for ratiometric electrochemical sensing of bisphenol A and S.

A novel ratiometric electrochemical sensor was developed based on a carbon cloth electrodeposited with silver nanoparticles and drop-coated by covalent organic framework (COF-LZU1) for simultaneous determination of bisphenol A (BPA) and bisphenol S (BPS). Carbon cloth exhibited a significantly larger electrochemical active area than common glassy carbon electrodes (27.5 times). Silver nanoparticles not only provided a stable reference signal but also enhanced electroactivity for the oxidation of BPA and BPS. COF-LZU1 with good adsorption performance and large periodic π-arrays promoted the enrichment of BPA and BPS to further increase the current response. Compared with the traditional single-signal electrochemical sensor, the developed ratiometric sensor exhibited better reproducibility and a wider linear range for BPA and BPS from 0.5 to 100 µM with a limit of detection of 0.15 µM. Furthermore, the developed sensor showed excellent stability and superior anti-interference ability. The real sample analysis for BPA and BPS has been successfully carried out in mineral water, electrolyte drink, tea, juice, and beer with recoveries of 88.3-111.7%. The developed ratiometric sensor is expected to be a candidate for the preparation of other electrochemical sensors and the analysis of additional practical samples.

Covalent organic framework DQTP modified pencil graphite electrode for simultaneous determination of bisphenol A and bisphenol S.

The sensitivity and selectivity of electrochemical analysis are challenging due to the materials used for electrode modification as well as electrical conductivity, catalytic activity and recognition ability of the working electrode. In this work, a portable 3D-printed electrochemical electrode clamp was designed and applied in combination with the developed covalent organic framework (COF DQTP)-modified pencil graphite electrode (DQTP/PGE). The ß-ketoenamine-linked COF DQTP synthesized by 1,3,5-triformylphloroglucinol (TP) and 2,6-diaminoanthraquinone (DQ) through solvothermal method is a porous crystalline with excellent conductivity and large periodic π-arrays, coupled with commercial available pencil graphite electrode to fabricate a disposable sensor for simultaneous determination of environmental endocrine disruptors bisphenol A and bisphenol S. The DQTP/PGE sensor exhibited high electrical conductivity and catalytic activity, and a good linearity was obtained in a range of 0.5-30 µM for two bisphenols with a detection limit of 0.15 µM (S/N = 3). Moreover, the sensor showed a reproducible and stable response over one month with negligible interference, and an accepted recovery with real food packaging samples.