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Sensitive surface-enhanced Raman scattering detection of atrazine based on aggregation of silver nanoparticles modified carbon dots
摘要： The development of precise detection methods with simply operation for pesticides in various environmental samples is a particular challenge. Here a highly sensitive surface-enhanced Raman scattering (SERS) approach for the selective detection of trace atrazine was proposed with R6G as a Raman reporter, which was adsorbed on silver nanoparticles modified carbon dots. The latter were prepared by the reduction of Ag+ by carbon dots. In the presence of atrazine, the aggregation of the modified carbon dots due to the interaction between silver nanoparticles and atrazine led to great enhancement of the SERS signal of R6G. Under optimal assay conditions, the limit of quantification was estimated to be 10 nM, which matched with the standard for drinking water quality of China and WHO defined limit. A good linear response to atrazine was found in the concentration range of 10-1000 nM with the relative standard deviations between 1.8% and 5.6%. The determination of atrazine in real water samples was also carried out to confirm the practicability of the proposed method, which showed the recoveries from 95% to 117.5%. The target induced aggregation for enhancing the signal offered great potential for sensitive on-site detection of atrazine in environments.
关键词： Silver nanoparticles,Pesticides,SERS detection,Target induced aggregation,Atrazine,Carbon dots
更新于2025-11-14 17:03:37
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A Simple Colorimetric and Fluorescent Sensor to Detect Organophosphate Pesticides Based on Adenosine Triphosphate-Modified Gold Nanoparticles
摘要： A simple and dual modal (colorimetric and fluorescent) sensor for organophosphate pesticides with high sensitivity and selectivity using adenosine triphosphate (ATP)- and rhodamine B-modified gold nanoparticles (RB-AuNPs), was successfully fabricated. This detection for ethoprophos afforded colorimetric and fluorescence imaging changes visualization. The quantitative determination was linearly proportional to the amounts of ethoprophos in the range of a micromolar scale (4.0–15.0 μM). The limit of detection for ethoprophos was as low as 37.0 nM at 3σ/k. Moreover, the extent application of this simple assay was successfully demonstrated in tap water samples with high reliability and applicability, indicating remarkable application in real samples.
关键词： multimodal assay,ethoprophos detection,gold nanoparticles,colorimetric and fluorescent sensor,organophosphate pesticides
更新于2025-09-23 15:23:52
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Structure-based design and application of an engineered glutathione transferase for the development of an optical biosensor for pesticides determination
摘要： In the present work, a structure-based design approach was used for the generation of a novel variant of synthetic glutathione transferase (PvGmGSTU) with higher sensitivity towards pesticides. Molecular modelling studies revealed Phe117 as a key residue that contributes to the formation of the hydrophobic binding site (H-site) and modulates the affinity of the enzyme towards xenobiotic compounds. Site-saturation mutagenesis of position Phe117 created a library of PvGmGSTU variants with altered kinetic and binding properties. Screening of the library against twenty-five different pesticides, showed that the mutant enzyme Phe117Ile displays 3-fold higher catalytic efficiency and exhibits increased affinity towards α-endosulfan, compared to the wild-type enzyme. Based on these catalytic features the mutant enzyme Phe117Ile was explored for the development of an optical biosensor for α-endosulfan. The enzyme was entrapped in alkosixylane sol-gel system in the presence of two pH indicators (bromocresol purple and phenol red). The sensing signal was based on the inhibition of the sol-gel entrapped GST, with subsequent decrease of released [H+] by the catalytic reaction, measured by sol–gel entrapped indicators. The assay response at 562 nm was linear in the range pH = 4–7. Linear calibration curves were obtained for α-endosulfan in the range of 0–30 μM. The reproducibility of the assay response, expressed by relative standard deviation, was in the order of 4.1% (N = 28). The method was successfully applied to the determination of α-endosulfan in real water samples without sample preparation steps.
关键词： Glutathione transferase,Biosensor,α-Endosulfan,Pesticides determination,Protein engineering
更新于2025-09-23 15:23:52
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In situ synthesis of gold nanoparticles on pseudo-paper films as flexible SERS substrate for sensitive detection of surface organic residues
摘要： Surface enhanced Raman scattering (SERS) substrates that can be attached to rough, irregular surfaces and directly collect samples is especially useful for the detection of surface organic residues. Herein, novel AuNPs-pseudo-paper films (APPFs) with uniform structure, flexible properties and wicking capabilities were first fabricated and used as SERS substrate for the sensitive detection of surface pesticides residues. Gold nanoparticles (AuNPs) were in situ synthesized on pseudo-paper films (PPFs) by iterative seeding method to create lots of “hot-spots”, accordingly exhibiting high SERS activity (SERS enhancement factor of 3.02×106). By virtue of polyethylenimine (PEI) grafted onto the dissolved microcrystalline cellulose (MCC), AuCl4- and AuNPs can firmly be bonded to the surfaces of PPFs. The prepared APPFs show high reproducibility (relative standard deviation of 6.13 %), which is attributed to the uniform surface of the films. The fabricated APPFs SERS substrate allows rapid detection of surface pesticides residues by a facile “swabbing-measure” detection mode avoiding tedious and time-consuming sampling and separation processes. Based on their inherent SERS spectra, thiram, parathion methyl, and malachite green (MG) can be simultaneously detected on apple peel, which demonstrates the potential applicability of this developed protocol for surface organic residues analysis in agriculture and food security.
关键词： surface pesticides residues,pseudo-paper,in situ synthesis,SERS
更新于2025-09-23 15:23:52
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Optimizing P25-rGO composites for pesticides degradation: Elucidation of photo-mechanism
摘要： The junction of graphene oxide with TiO2 particles can help develop more efficient photocatalysts capable to harvest radiation in a wider range of the electromagnetic spectrum for real photocatalytic applications. The synthesis procedure of TiO2 P25-rGO composites was optimized to photodegrade a selected mixture of pesticides classified by EU as priority pollutants (alachlor, diuron, atrazine and isoproturon). The influence of temperature and time of hydrothermal method, as well as the effect of graphene oxide (GO) percentage added in the synthesis, was studied to obtain the nanocomposite that showed the highest photoactivity. Long time and moderate temperature have offered the best interaction between TiO2 P25 and rGO. GO was quantitatively reduced to rGO during the hydrothermal treatment, but maintains a higher level of disorder. The optimal GO loading was found around 0.25 wt. %, which allowed the photocatalyst achieve high photocatalytic performance both in phenol and pesticides photodegradation. Finally, in order to try to elucidate the photocatalytic mechanism of the selected mixture of pesticides three scavengers were employed: methanol to scavenge hydroxyl radicals, formic acid for the photogenerated holes, and copper (II) nitrate to quench the electrons of the conduction band. In conclusion, all these pesticides were mostly photodegraded by the hydroxyl radicals (HO?) produced from the photo-induced holes (h+); given that the oxidant species generated from electrons or mediated by direct mechanism were not relevant.
关键词： Scavengers,TiO2P25-reduced graphene oxide composites,Pesticides,Photo-mechanism
更新于2025-09-23 15:23:52
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Signal enhancement in laser diode thermal desorption-triple quadrupole mass spectrometry analysis using microwell surface coatings
摘要： Laser diode thermal desorption (LDTD) is an ionization source usually coupled to triple quadrupole mass spectrometry (QqQMS) and specifically designed for laboratories requiring high-throughput analysis. It has been observed that surface coatings on LDTD microwell plates can improve the sensitivity of the analysis of small polar molecules. The objective of the present study is to understand and quantify the effect of microwell surface coatings on signal intensity of small organic molecules of clinical, environmental and forensic interest. Experiments showed that the peak areas of diclofenac, chloramphenicol, salicylic acid and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol obtained by LDTD-QqQMS increased by up to 3 orders of magnitude when using microwells coated with ethylenediaminetetraacetic acid (EDTA). Tests with different chelating agents and polytetrafluoroethylene as microwell surface coatings showed that nitrilotriacetic acid gave significantly higher peak areas for five out of the nine compounds that showed signal enhancement using chelating agents as coatings. Scanning electron microscopy studies of EDTA-coated and uncoated microwells showed that analytes deposited in the former formed more uniform and thinner films than in the latter. The enhancement effect of surface coatings in LDTD-QqQMS was explained mainly by the formation of homogenous and thinner layers of nanocrystals of analytes that are easier to desorb thermally than the layers formed when the analytes dry in direct contact with the bare stainless steel surface. Chemisorption of some analytes to the stainless steel surface of the microwell plate appeared to be a minor factor. Surface coatings widen the number of compounds analyzable by LDTD-QqQMS and can also improve sensitivity and limits of detection.
关键词： pharmaceuticals,high-throughput,hormones,pesticides,x-ray photoelectron spectroscopy,scanning electron microscopy,stainless steel,small organic molecules,chelating agents
更新于2025-09-23 15:23:52
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Surface Enhanced Raman Spectroscopy for In-Field Detection of Pesticides: A Test on Dimethoate Residues in Water and on Olive Leaves
摘要： Dimethoate (DMT) is an organophosphate insecticide commonly used to protect fruit trees and in particular olive trees. Since it is highly water-soluble, its use on olive trees is considered quite safe, because it flows away in the residual water during the oil extraction process. However, its use is strictly regulated, specially on organic cultures. The organic production chain certification is not trivial, since DMT rapidly degrades to omethoate (OMT) and both disappear in about two months. Therefore, simple, sensitive, cost-effective and accurate methods for the determination of dimethoate, possibly suitable for in-field application, can be of great interest. In this work, a quick screening method, possibly useful for organic cultures certification will be presented. DMT and OMT in water and on olive leaves have been detected by surface enhanced Raman spectroscopy (SERS) using portable instrumentations. On leaves, the SERS signals were measured with a reasonably good S/N ratio, allowing us to detect DMT at a concentration up to two orders of magnitude lower than the one usually recommended for in-field treatments. Moreover, detailed information on the DMT distribution on the leaves has been obtained by Raman line- (or area-) scanning experiments.
关键词： dimethoate,pesticides,SERS,portable microRaman,olive
更新于2025-09-19 17:15:36
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Rapid Detection of Pesticide Residues in Paddy Water Using Surface-Enhanced Raman Spectroscopy
摘要： Pesticide residue in paddy water is one of the main factors affecting the quality and safety of rice, however, the negative effect of this residue can be effectively prevented and reduced through early detection. This study developed a rapid detection method for fonofos, phosmet, and sulfoxaflor in paddy water through chemometric methods and surface-enhanced Raman spectroscopy (SERS). Residue from paddy water samples was directly used for SERS measurement. The obtained spectra from the SERS can detect 0.5 mg/L fonofos, 0.25 mg/L phosmet, and 1 mg/L sulfoxaflor through the appearance of major characteristic peaks. Then, we used chemometric methods to develop models for the intelligent analysis of pesticides, alongside the SERS spectra. The classification models developed by K-nearest neighbor identified all of the samples, with an accuracy of 100%. For the quantitative analysis, the partial least squares regression models obtained the best predicted performance for fonofos and sulfoxaflor, and the support vector machine model provided optimal results, with a root-mean-square error of validation of 0.207 and a coefficient of determination of validation of 0.99952, for phosmet. Experiments for actual contaminated samples also showed that the above models predicted the pesticide residue values with high accuracy. Overall, using SERS with chemometric methods provided a simple and convenient approach for the detection of pesticide residues in paddy water.
关键词： paddy water,SERS,pesticides,rapid detection
更新于2025-09-19 17:15:36
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Simulated revelation of the adsorption behaviours of acetylcholinesterase on charged self-assembled monolayers
摘要： An acetylcholinesterase (AChE)-based electrochemical biosensor, as a promising alternative to detect organophosphates (OPs) and carbamate pesticides, has gained considerable attention in recent years, due to the advantages of simplicity, rapidity, reliability and low cost. The bio-activity of AChE immobilized on the surface and the direct electron transfer (DET) rate between an enzyme and an electrode directly determined the analytical performances of the AChE-based biosensor, and experimental studies have shown that the charged surfaces have a strong impact on the detectability of the AChE-based biosensor. Therefore, it is very important to reveal the behaviour of AChE in bulk solution and on charged surfaces at the molecular level. In this work, the adsorption orientation and conformation of AChE from Torpedo californica (TcAChE) on oppositely charged self-assembled monolayers (SAMs), COOH-SAM and NH2-SAM with different surface charge densities, were investigated by parallel tempering Monte Carlo (PTMC) and all-atom molecular dynamics simulations (AAMD). Simulation results show that TcAChE could spontaneously and stably adsorb on two oppositely charged surfaces by the synergy of an electric dipole and charged residue patch, and opposite orientations were observed. The active-site gorge of TcAChE is oriented toward the surface with the “end-on” orientation and the active sites are close to the surface when it is adsorbed on the positively charged surface and the tunnel cost for the substrate is lower than that on the negatively charged surface and in bulk solution, while for TcAChE adsorbed on the negatively charged surface, the active site of TcAChE is far away from the surface and the active-site gorge is oriented toward the solution with a “back-on” orientation. It suggests that the positively charged surface could provide a better microenvironment for the efficient bio-catalytic reaction and quick DET between TcAChE and the electrode surface. Moreover, the RMSD, RMSF, dipole moment, gyration radius, eccentricity and superimposed structures show that only a slight conformational change occurred on the relatively flexible structure of TcAChE during simulations, and the native conformation is well preserved after adsorption. This work helps us better comprehend the adsorption mechanism of TcAChE on charged surfaces and might provide some guidelines for the development of new TcAChE-based amperometric biosensors for the detection of organophosphorus pesticides.
关键词： electrochemical biosensor,carbamate pesticides,molecular dynamics simulations,conformation,organophosphates,acetylcholinesterase,self-assembled monolayers,adsorption orientation
更新于2025-09-16 10:30:52
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Plasmon-active optical fiber functionalized by metal organic framework for pesticide detection
摘要： Functional plasmonic fiber for detection and on-line monitoring of organophosphorus pesticides in water or model soil samples is described. The appearance of the plasmon absorption band was realized through the deposition of a thin gold layer on the naked core of multimode optical fiber. The metalorganic frameworks (MOF-5) layer was deposited on the gold surface for the introduction of a high affinity towards the target pesticides. The MOF-5 layer affords the extraction of pesticides and their concentration primarily in the “plasmon evanescent wave” space, allowing the detection by the shift of plasmon absorption band. The growth of MOF-5 layer was confirmed using the Raman, XPS and XRD measurements. The entrapping of pesticides was checked using the Raman spectroscopy and ellipsometry, which also indicate the corresponding changes of MOF-5 refractive index. The series of further experiments demonstrate the applicability of proposed fiber sensor for detection of pesticides in soil without the false signals from surrounding media. The main advantages of proposed sensor can be attributed to simplicity, high sensitivity, low cost and the absence of organic solvents for the probe treatment.
关键词： Optical fiber,Organophosphorus pesticides detection,Metal–organic frameworks,Surface plasmon resonance,Sensor
更新于2025-09-12 10:27:22