Detection Of Organophosphorus Pesticides Research Articles

Surface-Enhanced Raman Spectroscopy Detection for Fenthion Pesticides Based on Gold Molecularly Imprinted Polymer Solid-State Substrates.

Current label-free surface-enhanced Raman spectroscopy (SERS) assay for the detection and analysis of organophosphorus pesticides has achieved initial success, but the application still faces constraints of substrate portability and specificity. To this end, this paper demonstrates a method for portable, rapid, and specific detection of low concentrations of fenthion pesticides based on a solid substrate of gold nanoparticle monolayers combined with molecularly imprinted polymers (MIPs). The nano-monolayers were transferred to the surface of mercapto-silicon wafers by interfacial self-assembly technique to form a stable connection with S-Au bonds and, at the same time, prevent nanoparticles from dropping off during the surfactant removal process. Then, the fenthion MIPs were directly generated on the surface of the monolayer film by spin-coating with a pre-polymerization solution and ultraviolet-induced polymerization. Tests showed that the molecular imprint was able to accurately bind to fenthion, but not other molecules, in a mixture of structural analogs, achieving a low concentration detection of 10-8 mol/L. The composite substrate maintained a signal uniformity of a relative standard deviation (RSD) = 7.05% and a batch-to-batch reproducibility of RSD = 10.40%, making it a potential pathway for the extended application of SERS technology.

Multifunctional 2D hemin-bridged MOF for the efficient removal and dual-mode detection of organophosphorus pesticides.

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied tothe efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7mgg-1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H2O2-directed transformation of 3,3',5,5'-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004nM and 0.02nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005nM and 0.04nM for colorimetric and photothermal methods, respectively. Theconstructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing.

Upconversion-based hydrogel kit with Python-assisted analysis platform for sample-to-result detection of organophosphorus pesticide

On-site quantitative analysis of pesticide residues is crucial for monitoring environmental quality and ensuring food safety. Herein, we have developed a reliable hydrogel portable kit using NaYbF4@NaYF4: Yb, Tm upconversion nanoparticles (UCNPs) combined with MnO2 nanoflakes. This portable kit is integrated with a smartphone reader and Python-assisted analysis platform to enable sample-to-result analysis for chlorpyrifos. The novel UCNPs maximizes energy donation to MnO2 acceptor by employing 100 % of activator Yb3+ in the nucleus for NIR excitation energy collection and confining emitter Tm3+ to the surface layer to shorten energy transfer distance. Under NIR excitation, efficient quenching of upconversion blue-violet emission by MnO2 nanoflakes occurs, and the quenched emission is recovered with acetylcholinesterase-mediated reactions. This process allows for the determination of chlorpyrifos by inhibiting enzymatic activity. The UCNPs/MnO2 were embedded to fabricate a hydrogel portable kit, the blue-violet emission images captured by smartphone were converted into corresponding gray values by Python-assisted superiority chart algorithm which achieves a real-time rapid quantitative analysis of chlorpyrifos with a detection limit of 0.17 ng mL−1. At the same time, pseudo-color images were also added by Python in “one run” to distinguish images clearly. This sensor detection with Python-assisted analysis platform provides a new perspective on pesticide monitoring and broadens the application prospects in bioanalysis.

PH-responsive dual-emission carbon dots for the ratiometric detection of organophosphorus pesticides in Brassica chinensis and Hg2+ in water

Accurate and rapid monitoring of organophosphorus pesticides (OPs) residues is crucial for regulating food safety. Herein, dual-emission carbon dots (de-CDs) were fabricated for the ratiometric detection of OPs and Hg2+. The de-CDs exhibited two emission peaks at 678 and 485 nm when excited with visible light. Interestingly, the fluorescence at 678 nm was significantly quenched by Hg2+ mainly because of the static quenching effect, whereas that at 485 nm exhibited a slight change. More significantly, the quenched fluorescence of the de-CDs recovered remarkably after introducing omethoate, diazinon and malathion. Accordingly, the ratiometric detection of the three OPs and Hg2+ was achieved with high selectivity and robust performance. In addition, the OPs residues assay in Brassica chinensis was successfully performed with satisfactory results. This study not only provides an attractive tool for the simple and rapid assay of OPs but also offers new insights into the fabrication of multi-functional carbon dots.

CdTe@ZnS quantum dots for rapid detection of organophosphorus pesticide in agricultural products

Organophosphorus pesticides (OPPs) constitute the most widely employed class of pesticides. However, the prevalent use of OPPs, while advantageous, raises concerns due to their toxicity, posing serious threats to food safety. Chemical sensors utilizing quantum dots (QDs) demonstrate promising applications in rapidly detecting OPPs residues, thereby facilitating efficient inspection of agricultural products. In this study, we employ an aqueous synthesis approach to prepare low toxic CdTe@ZnS QDs with stable fluorescence properties. To mitigate the risk of imprecise measurements stemming from the inherent susceptibility of fluorescence to quenching, we have adopted the principle of fluorescence resonance energy transfer (FRET) for the construction of the turn-on quantum dot sensor. With a detection limit for chlorpyrifos as low as 10 ppb (10 μg/L), the QDs sensor exhibits notable resistance to interference from various pesticides. Application of this system to detect organophosphorothioate pesticides in apples produced results consistent with those obtained from high-performance liquid chromatography (HPLC) detection, affirming the promising application prospects of this sensing system for the rapid detection of OPPs residues.

Universal organophosphate pesticides detection by peptide based fluorescent probes

In practical applications, the rapid and efficient detection of universal organophosphorus pesticides (OPs) can assist inspectors in quickly identifying the presence of OPs in samples. However, this presents a challenge for most well-established methods, typically designed to detect only a specific type of organophosphorus molecule at a time. In this proof-of-concept study, we draw inspiration from the structural similarities among OPs to develop innovative peptide-based fluorescence probes for the first time, which could efficiently detect a broad range of OPs within a mere 3 min. Analysis of fluorescence curve fitting reveals a clear linear correlation between the fluorescent intensity of the peptide probes and the concentration of OPs. Additionally, the selectivity analysis indicates that these peptide fluorescent probes exhibit an excellent response to various OPs while maintaining sufficient selectivity for detecting other pesticide types. Accurate sample analysis has also highlighted the potential of these peptide probes as practical tools for the rapid detection of OPs in actual vegetable samples. In summary, this proof-of-concept study presents an innovative approach to designing and developing ultrafast, universally peptide-based OP probes. These custom-designed peptide probes may facilitate rapid sample screening and offer initial quantification for OPs, potentially saving valuable time and effort in practical OP detection.

Platinum-nickel nanoparticle-based oxidase-like nanozyme for colorimetric/photothermal dual-mode detection of organophosphorus pesticides

In this study, based on the oxidase-like (OXD) activity of platinum-nickel nanoparticles (Pt-Ni NPs) nanozyme and further in collaboration with 3,3′,5,5′-tetramethylbenzidine (TMB), a colorimetric/photothermal dual-mode probe for organophosphorus pesticides (OPs) detection was developed. TMB undergone the catalytic oxidation of Pt-Ni NPs to change from colorless to blue oxidized substance (oxTMB) and exhibited higher temperature under near-infrared irradiation. The hydrolysis product of acid phosphatase (ACP) with L-ascorbic acid 2-phosphate trisodium competed with the OXD-like activity of Pt-Ni NPs to prevent the oxidation of TMB. As the concentration of OPs grew, inhibiting the blocking effect by deactivating ACP, the generated oxTMB caused notable color and temperature changes in the reaction system. The dual-mode probe responded linearly to chlorpyrifos, with the detection limits for colorimetric and photothermal modes of 1.2 ng/mL and 1.66 ng/mL, respectively. This work proposes a simple and reliable colorimetric/photothermal platform for OPs identification, which overcomes the problem that single-mode detection probes are susceptible to external factors, and has broad application potential in the field of food safety.

Sensitive fluorescence detection of glyphosate and glufosinate ammonium pesticides by purine-hydrazone-Cu2+ complex

Organophosphorus pesticides play an important role as broad-spectrum inactivating herbicides in agriculture. Developing a method for rapid and efficient organophosphorus pesticides detection is still urgent due to the increasing concern on food safety. An organo-probe (ZDA), synthesized by purine hydrazone derivative and 2,2′-dipyridylamine derivative, was applied in sensitive recognition of Cu2+ with detection limit of 300 nM. Mechanism study via density functional theory (DFT) and job’s plot experiment revealed that ZDA and Cu2+ ions form a 1:2 complex quenching the fluorescence emission. Moreover, this fluorescent complex ZDA-Cu2+ was applicable for detecting glyphosate and glufosinate ammonium following fluorescence enhancement mechanism, with detection limits of 11.26 nM and 11.5 nM, respectively. Meanwhile, ZDA-Cu2+ was effective and sensitive when it is used for pesticide detection, reaching the maximum value and stabilizing in 1 min. Finally, the ZDA-Cu2+ probe could also be tolerated in cell assay environment, implying potential bio-application.

Oxygen-doped ZnIn2S4 as a highly active and etchable photoactive material for chlorpyrifos detection

The development of a high-performance photoactive material and an effective and efficient analysis strategy are important for photoelectrochemical (PEC) analysis. We report here the enhanced PEC activity and etchable property of oxygen-doped ZnIn2S4 (O-ZnIn2S4) and its application for PEC detection of organophosphorus pesticides (OPs). O-ZnIn2S4 prepared by thermally treating ZnIn2S4 in air atmosphere can show much higher PEC activity than pristine ZnIn2S4, because oxygen doping can decrease the band gap and thereby increase the visible-light absorption. It is found that O-ZnIn2S4 can be etched by hydrogen peroxide, so O-ZnIn2S4 can be used for PEC analysis based on the etching strategy. Enzymatic reactions catalyzed by acetylcholinesterase and choline oxidase can produce hydrogen peroxide to etch the O-ZnIn2S4 modified on photoelectrode, so a “signal-off” state is achieved. OPs can inhibit the activity of acetylcholinesterase, and the etching of O-ZnIn2S4 is weakened, enabling “signal-on” PEC detection of OPs. Chlorpyrifos is selected as a model for PEC detection of OPs. The detection limit for chlorpyrifos detection is 2 × 10−4 mg L−1 with a linear range from 0.001 to 50 mg L−1. The present study not only develops a high-performance photoactive material for PEC analysis but also provides an efficient PEC sensing strategy based on ZnIn2S4 etching.

2D magnetic nanoporous carbon with bridge-type aptamer assembly for pesticide detection based on a regenerative field-effect transistor biosensor

Field-effect transistor (FET)-based biosensors have garnered attention due to their sensitivity to surface charge changes and advantages in real-time detection. However, these biosensors often suffer from several disadvantages such as their limited sensitivity and a high cost. Here, we reported an ultra-sensitive and reusable nanoporous-based FET biosensor hybridized with bridge-type aptamers. The sensor consisted of a two-dimensional magnetic iron-cobalt nanoparticle-embedded nanoporous carbon (Fe-Co/NPC) functionalized with bridge-type aptamers. The edges of the nanopores exhibited high surface energy and chemical activity, enabling effective interactions with the aptamers. Moreover, the nanoporous structures provided additional space, which could improve molecular recognition sites and sensor sensitivity. Our sensor could be used to detect organophosphorus pesticides (OPs) in vegetables down to 100 fM in real time and identify OPs from other pesticides. Furthermore, the magnetic properties of Fe-Co/NPC allowed us to reuse a single sensor chip up to 8 times, which significantly reduced the production cost of our sensors. In this respect, our Fe-Co/NPC-FET sensor could be a powerful tool for practical applications such as food safety detection.

Detection of organophosphorus pesticides by a fluorescent sensing assay coupled with enzyme inhibition

Glyphosate (Gly), as a common organophosphorus pesticides (OPs), is being overly put into usage and it should be monitored in a timely manner. Herein, optically well-performing quantum dots (QDs) were prepared by hydrothermal synthesis to create a fluorescent sensing assay that responds to OPs and quantitatively detects Gly. The mechanism of sensing is based on OPs inhibiting enzyme activity and accompanying pH changes in the system. It can respond to multiple OPs (trichlorphon, methamidophos and chlorpyrifos). Particularly, the quantification of Gly is outstanding with a detection range of 0.2 ∼ 1.8 mg/L and the detection limit as low as 0.015 mg/L. This system has not only good selectivity and repeatability, but also reliable application potential. In spiked experiments, a recovery of 96.50∼107.00% was demonstrated. Fluorescent sensing assay coupled with enzyme inhibition provides a novel choice for pesticide detection and offers considerable value in related fields.

Developing a magnetic SERS nanosensor utilizing aminated Fe-Based MOF for ultrasensitive trace detection of organophosphorus pesticides in apple juice

The unreasonable use of organophosphorus pesticides leads to excessive pesticide residues in food, seriously threatening public health, and the potential of surface-enhanced Raman spectroscopy (SERS) technology, incorporating a metal–organic framework, is substantial for the rapid detection of trace pesticide residues. Here, a novel Fe3O4@NH2-MIL-101(Fe)@Ag (FNMA) SERS nanosensor was developed. Results indicated that the FNMA had a high enhancement factor of 1.53 × 108, a low limit of detection (LOD) of 4.55 × 10−12 M, and a relative standard deviation of 7.73 % for 4-nitrothiophenol, demonstrating its good SERS sensitivity and uniformity, and also possessed good storage stability for one month. In quantifying fenthion and methyl parathion in standard solutions and apple juice in the range of 0.05/0.02–20 mg/L, it showed LODs of 3.02 × 10−3 mg/L and 1.43 × 10−3 mg/L, and 0.0407 and 0.0075 mg/L, respectively, demonstrating potentials in ultrasensitive trace detection of pesticides in food.

Wool keratin-based colorimetric detection of organophosphorus pesticides via a multi-enzyme cascade reaction

Wool keratin-based colorimetric detection of organophosphorus pesticides via a multi-enzyme cascade reaction

Mn-modified porphyrin metal–organic framework mediated colorimetric and photothermal dual-channel probe for sensitive detection of organophosphorus pesticides

Herein, a novel dual-mode probe for organophosphorus pesticides (OPs) colorimetric and photothermal detection was developed based on manganese modified porphyrin metal–organic framework (PCN-224-Mn). PCN-224-Mn had excellent oxidase-like activity and oxidized colorless 3,3,5,5-tetramethylbenzidine (TMB) to blue–green oxidation state TMB (oxTMB), which exhibited high temperature under near-infrared irradiation. l-ascorbate-2-phosphate was hydrolyzed by acid phosphatase to produce ascorbic acid, which weakened colorimetric and photothermal signals by impacting oxTMB generation. The presence of OPs blocked the production of ascorbic acid by irreversibly inhibiting the activity of acid phosphatase, causing the restoration of chromogenic reaction and the increase of temperature. Under the optimal conditions, the probe showed a good linear response to OPs in the concentration range of 5 ∼ 10000 ng/mL, using glyphosate as the analog. The detection limits of glyphosate in colorimetric mode and photothermal mode were 1.47 ng/mL and 2.00 ng/mL, respectively. The probe was successfully used for sensitive identification of OPs residues in tea, brown rice, and wheat flour. This work proposes a simple and reliable colorimetric/photothermal platform for OPs identification, which overcomes the problem that single-mode detection probes are susceptible to external factors, and has broad application potential in the field of food safety.

A Multienzyme Reaction-Mediated Electrochemical Biosensor for Sensitive Detection of Organophosphorus Pesticides.

Ethephon (ETH), a commonly employed growth regulator, poses potential health risks due to its residue in fruits and vegetables, leading to both acute and subchronic toxicity. However, the detection accuracy of ETH is compromised by the color effects of the samples during the detection process. In this work, a multienzyme reaction-mediated electrochemical biosensor (MRMEC) was developed for the sensitive, rapid, and color-interference-resistant determination of ETH. Nanozymes Fe3O4@Au-Pt and graphene nanocomplexes (GN-Au NPs) were prepared as catalysts and signal amplifiers for MRMEC. Acetylcholinesterase (AChE), acetylcholine (ACh), and choline oxidase (CHOx) form a cascade enzyme reaction to produce H2O2 in an electrolytic cell. Fe3O4@Au-Pt has excellent peroxidase-like activity and can catalyze the oxidation of 3,3',5,5'-tetramethvlbenzidine (TMB) in the presence of H2O2, resulting in a decrease in the characteristic peak current of TMB. Based on the inhibitory effect of ETH on AChE, the differential pulse voltammetry (DPV) current signal of TMB was used to detect ETH, offering the limit of detection (LOD) of 2.01 nmol L-1. The MRMEC method effectively analyzed ETH levels in mangoes, showing satisfactory precision (coefficient of variations, 2.88-15.97%) and recovery rate (92.18-110.72%). This biosensor holds promise for detecting various organophosphorus pesticides in food samples.

Smartphone-assisted colorimetric biosensor for the determination of organophosphorus pesticides on the peel of fruits

Nowadays, the widespread use of organophosphorus pesticides (OPs) in agricultural production leads to varying degrees of residues in crops, which pose a potential threat to human health. Conventional methods used in national standard for the detection of OPs in fruits and vegetables require expensive instruments or cumbersome sample pretreatment steps for the analysis. To address these challenges, in this work, we took advantage of the peroxidase-like activity of PtCu3 alloy nanocrystals (NCs) for a colorimetric and smartphone assisted sensitive detection of OPs. With the assist of a smartphone, the concentration of OPs on the peel of fruits could be obtained by comparing the B/RG value (the brightness value of blue divided by those of red and green) of a test strip with a calibration curve. This work not only provides a facile and cost-effective method to detect pesticides but also makes a positive contribution to food safety warning.

A MOF nanozyme-mediated acetylcholinesterase-free colorimetric strategy for direct detection of organophosphorus pesticides.

Although some simple and rapid colorimetric methods have been developed to detect organophosphorus pesticides (OPs), the difficult extraction and easy denaturation of acetylcholinesterase (AChE) are still drawbacks needing to be overcome. Here, we propose a MOF nanozyme-mediated AChE-free colorimetric strategy for the direct detection of OPs. In the presence of OPs (pirimiphos-methyl as a model), the intense blue of oxidized 3,3',5,5'-tetramethylbenzidine (TMB) becomes light due to the quenching effect of OPs towards hydroxyl radicals (˙OH) that are generated by the decomposition of H2O2 catalyzed by the Cu4Co6 ZIF nanozyme with excellent peroxidase (POD)-like activity. The developed colorimetric sensor exhibits assay performance and offers a universal and promising analysis strategy for detecting OPs in practical samples.

A MnO2 nanosheet-mediated CRISPR/Cas12a system for the detection of organophosphorus pesticides in environmental water.

Nowadays, easy, convenient, and sensitive sensing strategies are still critical for organophosphorus pesticides in environmental water samples. Herein, a novel organophosphorus pesticide (OP) assay based on acetylcholinesterase (AChE) and a MnO2 nanosheet-mediated CRISPR/Cas12a reaction is reported. The single-strand DNA (ssDNA) activator of CRISPR/Cas12a was simply adsorbed on the MnO2 nanosheets as the nanoswitches of the assay. In the absence of target OPs, AChE hydrolyzed acetylcholine (ATCh) to thiocholine (TCh), which reduced the MnO2 nanosheets to Mn2+, resulting in the release of the activator followed by activation of the CRISPR/Cas12a system. The activated Cas12a thereafter nonspecifically cleaved the FAM/BHQ1-labeled ssDNA (FQ-reporter), producing a fluorescence signal. Upon the addition of target OPs, the hydrolysis of ATCh by AChE was inhibited owing to OPs combining with AChE, and thus effective quantification of OPs could be achieved by measuring the fluorescence changes of the system. As a proof of concept, dichlorvos (DDVP) was chosen as a model OP analyte to address the feasibility of the proposed method. Attributed to the excellent trans-cleavage activity of Cas12a, the fluorescent biosensor exhibits a satisfactory limit of detection (LOD) for DDVP at 0.135 ng mL-1. In addition, the excellent recoveries for the detection of DDVP in environmental water samples demonstrate the applicability of the proposed assay in real sample research.

Magical Pesticide Residue Detection Test Strips: Aptamer-based Lateral Flow Test Strips for Organophosphorus Pesticide Detection

Magical Pesticide Residue Detection Test Strips: Aptamer-based Lateral Flow Test Strips for Organophosphorus Pesticide Detection

Development of a bioluminescence resonance energy transfer Quenchbody sensor for the detection of organophosphorus pesticides in water bodies

Rapid and precise quantification of organophosphorus pesticides (OPPs) in environmental water bodies is crucial for evaluating ecological risks and safeguarding human health. Traditional instrumental methods are complex, time-consuming, and expensive, while enzyme-based biosensors suffer from instability and require a constant supply of substrates. Hence, there is an urgent need for a fast, simple, and sensitive biosensor for OPPs. In this study, we developed a novel non-enzymatic biosensor for the detection of methyl parathion (MP) by employing the bioluminescence resonance energy transfer (BRET) Q-body strategy. Optimizing the spacer arm and screening fluorescent dyes identified the R6G BRET MP Q-body sensor with the best performance. Key parameters affecting the sensor's detection performance were optimized by using single-factor experiments. Under optimal conditions, the detection exhibited a detection limit of 5.09 ng·mL−1 and a linear range of 16.21–848.81 ng·mL−1. The sensor's accuracy was validated using standard recovery experiments, yielding a recovery rate of 84.47 %–102.08 % with a standard deviation of 1.93 %–9.25 %. The detection results of actual water samples demonstrate that this fast, simple, and highly sensitive BRET Q-body sensor holds great promise for practical water quality monitoring.