Construction of coumarin-appended calix[4]arene-based fluorescence sensor for the detection of carbofuran in cabbage.

This study presents a novel approach for the detection of carbofuran (CBF) insecticide by systematically exploring a calix[4]arene-derived fluorescence probe, CouC4S, functionalized with two coumarin-labelled cystamine linkages at the narrow edge of the calix[4]arene platform. The proposed method showed a fluorescence "signal - off" effect when CBF binds with CouC4S by quenching the fluorescence intensity of CouC4S. Its limit of detection was as low as 5.55 µM according to the emission study. The working concentration range for this ligand was observed to be up to 5-65 µM. This method could be applied for the on-spot detection of CBF in real samples such as cabbage by spiking CBFvia in situ experiments, which exhibited a limit of detection of 8.823 ppm. For the further confirmation of CouC4S:CBF binding, cyclic voltammetry, differential pulse voltammetry, powder X-ray diffraction, FT-IR spectroscopy, 1H NMR titration, MALDI-TOF and computational investigations were carried out.

Expeditive carbofuran pesticide degradation by submerged thermal plasma and its accelerated mineralization by persulfate addition.

Rapid degradation of carbofuran (CBF) pesticide is effectively achieved by submerged thermal plasma (STP) without and with the addition of persulfate (PS) at two different concentrations (10 and 20 ppm). Degradation efficiency was examined using high-performance liquid chromatography (HPLC), and mineralization percentage was determined by total organic carbon (TOC) analysis. Adding 10 ppm PS showed higher degradation and mineralization percentages of 99.5% and 65.2%, respectively, than mere plasma treatment and 20 ppm PS addition to CBF solution. A relatively higher energy yield of 40 mg/kWh and a first order kinetic reaction rate of 0.262 min-1 were obtained in the 10 PS added STP treatment. Liquid chromatography mass spectrometry (LCMS) analysis illustrated reaction intermediates formed during plasma treatment. Scavenger investigation implied that •OH radical is the prime cause of CBF degradation, as degradation percentage declined to 50% in all conditions. Toxicity assessment of CBF and its degradation products was predicted using Toxicity estimation software tool (TEST), and plasma treated solutions (PTS) were experimentally investigated on Eudrilus eugeniae earthworms by monitoring its mortality rate, self-assemblage, and histopathological analysis. A lower mortality rate (46%) and self-assemblage (167 s) of earthworms were detected for plasma treated CBF than for the other conditions. The results reveal that PTS is less toxic for earthworms than untreated CBF solution. These findings imply that STP is an effective technique for bio-recalcitrant pollutants degradation in agrochemical industries.

Degradation of carbofuran and acetamiprid in wolfberry by dielectric barrier discharge plasma: Kinetics, pathways, toxicity and molecular dynamics simulation.

Carbofuran and acetamiprid pose the highest residual risk among pesticides found in wolfberries. This study aimed to degrade these pesticides in wolfberries using a multi-array dielectric barrier discharge plasma (DBD), evaluate the impact on safety and quality and explore their degradation mechanism. The results showed that DBD treatment achieved 90.6% and 80.9% degradation rates for carbofuran and acetamiprid, respectively, following a first-order kinetic reaction. The 120 s treatment successfully reduced pesticide contamination to levels below maximum residue limits. Treatment up to 180 s did not adversely affect the quality of wolfberries. QTOF/MS identification and degradation pathway analysis revealed that DBD broke down the furan ring and carbamate group of carbofuran, while replacing the chlorine atom and oxidizing the side chain of acetamiprid, leading to degradation. The toxicological evaluation showed that the degradation products were less toxic than undegraded pesticides. Molecular dynamics simulations revealed the reactive oxygen species (ROS) facilitated the degradation of pesticides through dehydrogenation and radical addition reactions. ROS type and dosage significantly affected the breakage of chemical bonds associated with toxicity (C4-O5 and C2-Cl1). These findings deepen insights into the plasma chemical degradation of pesticides.

Coupling pathway prediction and fluorescence spectroscopy to assess the impact of auxiliary substrates on micropollutant biodegradation.

Some bacteria can degrade organic micropollutants (OMPs) as primary carbon sources. Due to typically low OMP concentrations, these bacteria may benefit from supplemental assimilation of natural substrates present in the pool of dissolved organic matter (DOM). The biodegradability of such auxiliary substrates and the impacts on OMP removal are tightly linked to biotransformation pathways. Here, we aimed to elucidate the biodegradability and effect of different DOM constituents for the carbofuran degrader Novosphingobium sp. KN65.2, using a novel approach that combines pathway prediction, laboratory experiments, and fluorescence spectroscopy. Pathway prediction suggested that ring hydroxylation reactions catalysed by Rieske-type dioxygenases and flavin-dependent monooxygenases determine the transformability of the 11 aromatic compounds used as model DOM constituents. Our approach further identified two groups with distinct transformation mechanisms amongst the four growth-supporting compounds selected for mixed substrate biodegradation experiments with the pesticide carbofuran (Group 1: 4-hydroxybenzoic acid, 4-hydroxybenzaldehyde; Group 2: p-coumaric acid, ferulic acid). Carbofuran biodegradation kinetics were stable in the presence of both Group 1 and Group 2 auxiliary substrates. However, Group 2 substrates would be preferable for bioremediation processes, as they showed constant biodegradation kinetics under different experimental conditions (pre-growing KN65.2 on carbofuran vs. DOM constituent). Furthermore, Group 2 substrates were utilisable by KN65.2 in the presence of a competitor (Pseudomonas fluorescens sp. P17). Our study thus presents a simple and cost-efficient approach that reveals mechanistic insights into OMP-DOM biodegradation.

Paper-based colorimetric sensor using Photoshop and a smartphone app for the quantitative detection of carbofuran.

We developed a smartphone-assisted microchemistry analyzer for the quantitative detection of carbofuran using a paper-based colorimetric sensor, Photoshop software, and a smartphone app. The changes in color of the carbofuran enzymatic reaction in the paper-based sensor were captured and analyzed using a smartphone-controlled analyzer with an LED light source and a smartphone camera. The high accuracy of this method was demonstrated for the determination of carbofuran with a linear response in the range 0.05-1.0 ppm and limits of detection (LOD) of 0.02 and 0.018 ppm using Photoshop and smartphone app colorimetric analysis, respectively. These two methods not only show the high sensitivity and highly quantitative relationships between the concentrations of commercial carbofuran and characteristic color values of the blue channel in smartphone images but were also applied to infusions of tea. Moreover, the smartphone app is able to GPS tag the location of the test and transmit the results to a website that displays quantitative results from carbofuran samples on a map.

Sublethal toxicity of carbofuran in cattle egret (Bubulcus ibis coromandus): hematological, biochemical, and histopathological alterations / Toxicidade subletal do carbofurano na garça-vaqueira (Bubulcus ibis coromandus): alterações hematológicas, bioquímicas e histopatológicas

Abstract This study was aimed to investigate Carbofuran (CF)-induced pathological changes in cattle egret. Two hundred cattle egrets were reared and equally divided into four groups and given different CF concentrations (0.03 mg/L, 0.02 mg/L, 0.01 mg/L and 0 mg/L (control group)). Hematology, serum biochemistry, histopathology, and immunological markers were studied. Our results confirm that CF induces anemic conditions, leukocytosis, elevated liver enzymatic activity, and alterations in renal biomarkers. Moreover, specific microscopic lesions such as multifocal necrosis, pyknotic nuclei, hemorrhages, congestion, and inflammatory cell proliferation were observed in the liver, kidney, spleen, and thymus. These findings suggest that CF can induce harmful effects, so the application of this pesticide in the field must be strictly monitored to mitigate the possibility of exposure to non-target species.

Resumo Este estudo teve como objetivo investigar as alterações patológicas induzidas por carbofurano (CF) em garças-vaqueiras. Duzentas dessas garças foram criadas e divididas igualmente em quatro grupos e receberam diferentes concentrações de CF: 0,03 mg/L; 0,02 mg/L; 0,01 mg/L; e 0 mg/L (grupo controle). Foram realizadas análises de hematologia, bioquímica sérica, histopatologia e marcadores imunológicos. Nossos resultados confirmaram que CF induz condições anêmicas, leucocitose, atividade enzimática hepática elevada e alterações nos biomarcadores renais. Além disso, lesões microscópicas específicas, como necrose multifocal, núcleos picnóticos, hemorragias, congestão e proliferação de células inflamatórias, foram observadas no fígado, rim, baço e timo. Esses achados sugerem que o CF pode causar efeitos nocivos, portanto a aplicação desse agrotóxico no campo deve ser rigorosamente monitorada para mitigar a possibilidade de exposição a espécies não alvo.

Noncovalent binding of carbofuran to acetylcholinesterase from Homo sapiens, Danio rerio, Apis mellifera and Caenorhabditis elegans: Homology modelling, molecular docking and dynamics, and quantum biochemistry description.

Although various regulatory agencies have banned or severely restricted the use of carbofuran (CAR), recent reports indicate the presence of CAR residues in both cultivated and wild areas. This pesticide is a potent inhibitor of acetylcholinesterase (AChE), which acts by preventing the hydrolysis of acetylcholine (ACh). Given the critical role of AChE::ACh in the proper functioning of the nervous system, we thought it appropriate to investigate the binding of CAR to AChEs from Homo sapiens, Danio rerio, Apis mellifera, and Caenorhabditis elegans using homology modelling, molecular docking, molecular dynamics, and quantum biochemistry. Molecular docking and dynamics results indicated peculiar structural behavior in each AChE::CAR system. Quantum biochemistry results showed similar affinities for all complexes, confirming the description of carbofuran as a broad-spectrum pesticide, and have a limited correlation with IC50 values. We found the following decreasing affinity order of AChE species: H. sapiens > A. mellifera > C. elegans > D. rerio. The computational results suggest that CAR occupies different pockets in the AChEs studied. In addition, our results showed that CAR binds to hsAChE and ceAChE in a very similar manner: it has high affinities for the same subsites in both species and forms hydrogen bonds with residues (hsTYR124 and ceTRP107) occupying homologous positions in the peripheral site. This suggests that this nematode is a potential model to evaluate the toxicity of carbamates, even though the sequence identity between them is only 41 %. Interestingly, we also observed that the catalytic histidines of drAChE and amAChE exhibited favorable contacts with carbofuran, suggesting that the non-covalent binding of carbofuran to these proteins may promote faster carbamylation rates than the binding modes to human and worm acetylcholinesterases. Our computational results provide a better understanding of the binding mechanisms in these complexes, as well as new insights into the mechanism of carbamylation.

The adsorption effects of biochar on carbofuran in water and the mixture toxicity of biochar-carbofuran in rats.

Carbofuran, a widely used carbamate insecticide, is frequently detected in water. In this study, a high-performance adsorbent (WAB4) for carbofuran was obtained from laboratory-synthesized biochars. The maximum adsorption of carbofuran by WAB4 reaches 113.7 mg/g approximately. The adsorption of carbofuran by biochar was a multi-molecular layer and the adsorption process conforms to the pseudo-second-order kinetic model (R2 = 0.9984) and Freundlich isotherm model (R2 = 0.99). Importantly, an in vivo rat model was used to assess the combined toxicological effects of biochar-carbofuran complexes. The toxicity of the complexes (LD50 > 12 mg/kg) is lower than that of carbofuran (LD50 = 7.9 mg/kg) alone. The damage of biochar-carbofuran complex on rat liver and lung is significantly less than that of carbofuran. The Cmax and bioavailability of carbofuran were found to be reduced by 64% and 68%, respectively, when biochar was present, by UPLC-MS/MS analysis of carbofuran in rat plasma. Furthermore, it was confirmed that the biochar-carbofuran complex is relatively stable in the gastrointestinal tract, by performing a carbofuran release assay in artificial gastrointestinal fluids in vitro. Collectively, biochar is a bio-friendly material for the removal of carbofuran from water.

Effects of the Pesticide Carbofuran on Two Species of Chlorophyceae (Desmodesmus communis and Pseudopediastrum boryanum) and Their Pesticide Bioremediation Ability.

Carbofuran is one of the most toxic broad-spectrum pesticides. We evaluated the effects of carbofuran on two species of microalgae, Pseudopediastrum boryanum and Desmodesmus communis, through measurements of cell viability, biomass, chlorophyll content, and the production of reactive oxygen species (ROS). The ability of these algae to remove carbofuran dissolved in the media was also determined. For the evaluations, both microalgae species were exposed to carbofuran (FURADAN 350 SC®) at concentrations of 100, 1000, and 10,000 µg L-1 for 7 days. Algae cell viability and chlorophyll-a concentration were not affected by the presence of carbofuran. Both species grew when exposed to the pesticide; however, the microalgae D. communis grew less than its respective control when exposed to the highest concentration (10,000 µg L-1 of carbofuran), indicating an adverse effect of the pesticide on this species. A significant increase in ROS production was observed in D. communis and P. boryanum when exposed to the highest concentration tested. The microalgae P. boryanum completely removed carbofuran in the media within 2 days, regardless of the concentration, whereas D. communis achieved the same result only after 5 days of exposure. Growth inhibition was observed only until the disappearance of carbofuran from the media. The present study suggests the use of microalgae, mainly P. boryanum, as potential tools for the remediation of environments contaminated by carbofuran because of their resistance to the insecticide and their ability to remove it rapidly from water. Environ Toxicol Chem 2024;43:926-937. © 2023 SETAC.

Biodegradation of carbofuran by Pseudomonas aeruginosa S07: biosurfactant production, plant growth promotion, and metal tolerance.

Pesticides are an indispensable part of modern farming as it aids in controlling pests and hence increase crop yield. But, unmanaged use of pesticides is a growing concern for safety and conservation of the environment. In the present study, a novel biosurfactant-producing bacterium, Pseudomonas aeruginosa S07, was utilized to degrade carbofuran pesticide, and it was obtained at 150 mg/L concentration; 89.2% degradation was achieved on the 5th day of incubation in in vitro culture condition. GC-MS (gas chromatography and mass spectrometry) and LC-MS (liquid chromatography and mass spectrometry) analyses revealed the presence of several degradation intermediates such as hydroxycarbofurnan, ketocarbofuran, and hydroxybenzofuran, in the degradation process. The bacterium was found to exhibit tolerance towards several heavy metals: Cu, Co, Zn, Ni, and Cd, where maximum and least tolerance were obtained against Co and Ni, respectively. Additionally, the bacterium also possesses plant growth-promoting activity showing positive results in nitrogen fixation, phosphate solubilising, ammonia production, and potassium solubilizing assays. Thus, from the study, it can be assumed that the bacterium can be useful in the production of bioformulation for remediation and rejuvenation of pesticide-contaminated sites in the coming days.

An electrochemical aptasensor for detection of carbofuran using gold nanoparticles decorated hierarchical porous carbon as an effective sensing platform.

In this study, a novel electrochemical aptasensor for carbofuran (CBF) detection is prepared by gold nanoparticles decorated hierarchical porous carbon (Au@HPC). The prepared carbon materials show a three-dimensional hierarchical structure with a large specific surface area and a highly developed porous structure. Aptamers loading significantly improves when gold nanoparticles are embedded into the hierarchical porous carbon skeleton. Besides, Au@HPC modified electrode exhibits a large electroactive area and excellent electrochemical conductivity, serving as a promising platform for highly sensitive and selective electrochemical detection of CBF. The developed CBF electrochemical aptasensor shows a wide linear from 1.0 to 100000 pg/L with a detection limit of 0.5 pg/L, demonstrating an extraordinary sensitivity compared to other sensors for CBF detection. Additionally, the designed aptasensor was used to monitor the CBF in vegetable samples, with a recovery range from 98.4% to 104.8%. The results coincide with the standard test method, revealing its practicability in the food safety analysis.

Cobalt ferrite/semiconducting single-walled carbon nanotubes based field-effect transistor for determination of carbamate pesticides.

Carbaryl and carbofuran are the carbamate pesticides which have been widely used worldwide to control insects in crops and house. If the pesticides entered in to the food products and drinking water, they could cause serious health effects in humans. Therefore, the development of a rapid, simple, sensitive and selective analytical device for on-site detection of carbamates is crucial to evaluate food and environmental samples. Recently, semiconducting single-walled carbon nanotube-based field effect transistors (s-SWCNT/FETs) have shown several advantages such as high carrier mobility, good on/off ratio, quasi ballistic electron transport, label-free detection and real-time response. Herein, cobalt ferrite (CFO) nanoparticles decorated s-SWCNTs have been prepared and used to bridge the source and drain electrodes. As-prepared CFO/s-SWCNT/FET had been used for the non-enzymatic detection of carbaryl and carbofuran. When used as a sensing platform, the CFO/s-SWCNT hybrid film exhibited high sensitivity, and selectivity with a wide linear range of detection from 10 to 100 fMand the lowest limit of detections for carbaryl (0.11 fM) and carbofuran (0.07 fM) were estimated. This sensor was also used to detect carbaryl in tomato and cabbage samples, which confirmed its practical acceptance. Such performance may be attributed to the oxidation of carbamates by potent catalytic activity of CFO, which led to the changes in the charge transfer reaction on the s-SWCNTs/FET conduction channel. This work presents a novel CFO/s-SWCNT based sensing system which could be used to quantify pesticide residues in food samples.

Inter-species differences between humans and other mammals in the in vitro metabolism of carbofuran and the role of human CYP enzymes.

This study investigated the metabolic transformation of carbofuran in seven species of mammals using LC-MS/MS and liver microsomes. The results revealed species-specific differences in metabolite formation, indicating the potential role of metabolic pathways in toxicity and risk assessment. The majority of carbofuran was metabolized through the 3-hydroxycarbofuran pathway, with the highest levels observed in dogLM and the lowest in humanLM. Further analysis was conducted to investigate the human cytochrome P450-mediated metabolism of carbofuran, with CYP3A4 being found to be the most efficient enzyme with the highest contribution to the 3-hydroxycarbofuran pathway. Inhibition of CYP3A4 with ketoconazole resulted in a substantial decrease in carbofuran metabolism. In addition, carbofuran exhibited inhibitory effects on human CYP3A4 and CYP2B6, demonstrating the potential for carbofuran to interact with these enzymes. The findings highlight the importance of in vitro screening for metabolic processes and provide insights into the biotransformation of carbofuran.

Exorbitant signatures of pesticides and pharmaceuticals in municipal solid wastes (MSWs): Novel insights through risk analysis, dissolution dynamics, and model-based source identification.

Studies on the occurrence and fates of emerging organic micropollutants (EOMPs) like pharmaceuticals and pesticides in MSWs are scarce in the literature. Therefore, MSWs were sampled from 20 Indian landfills and characterized for five widely consumed EOMPs (chlorpyrifos, cypermethrin, carbofuran, carbamazepine, and sodium diclofenac), physicochemical, and biological properties. The pesticide (median: 0.17-0.44 mg kg-1) and pharmaceutical (median: 0.20-0.26 mg kg-1) concentrations significantly fluctuated based on landfill localities. Eventually, principal component and multi-factor (MFA) models demonstrated close interactions of EOMPs with biological (microbial biomass and humification rates) and chemical (N, P, K, Ca, S, etc.) properties of MSWs. At the same time, the MFA resolved that EOMPs' fates in MSWs significantly differ from bigger cosmopolitan cities to smaller rural townships. Correspondingly, the concentration-driven ecological risks were high in 15 MSWs with EOMP-toxicity ranks of diclofenac > carbofuran = chlorpyrifos > cypermethrin > carbamazepine. The EOMPs' dissolution dynamics and source apportionments were evaluated using the positive matrix factorization (PMF) model for the first time on experimental data, extracting four anthropogenic sources (households, heterogeneous business centers, agricultural, and open drains). The most significant contribution of EOMPs to MSWs was due to heterogeneous business activity. Notably, the aging of soluble chemical fractions seems to influence the source characteristics of EOMPs strongly.

A retrospective screening method for carbamate toxicant exposure based on butyrylcholinesterase adducts in human plasma with ultra-high performance liquid chromatography-tandem mass spectrometry.

Carbamate pesticides are extensively used in agriculture for their inhibition to acetylcholinesterase and damages to the insects' neural systems. Because of their toxicity, human poisoning incidents caused by carbamate pesticide exposure have occurred from time to time. What's more, some lethally toxic carbamate toxicants known as carbamate nerve agents (CMNAs) have been supplemented in Schedule 1 of the Annex on Chemicals in the Chemical Weapons Convention (CWC) by Organisation of the Prohibition of Chemical Weapons (OPCW) from 2020. And some other carbamates, like physostigmine, have been used in clinical treatment as anticholinergic drugs and their misuse may also cause damages to the body. Similar to organophosphorus toxicants, carbamate toxicants would react with butyrylcholinesterase (BChE) in plasma when entering the human body, resulting in the BChE adducts, based on which the exposure of carbamate toxicants could be detected retrospectively. In this study, methylcarbamyl nonapeptide and dimethylcarbamyl nonapeptide from pepsin digestion of BChE adducts were identified with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) in product ion scan mode. Carbofuran was chosen as the target to establish the detection method of carbamate toxicant exposure based on methylcarbamyl nonapeptide digested from methylcarbamyl BChE. Procainamide-gel affinity purification, pepsin digestion and UHPLC-MS/MS analysis in multiple reaction monitoring (MRM) mode were applied. Under the optimized conditions of sample preparation and UHPLC-MS/MS MRM analysis, the limits of detection (LODs) reached 10.0 ng/mL of plasma exposed to carbofuran with satisfactory specificity. The quantitation approach was established with d3-carbofuran-exposed plasma as the internal standard (IS) and the linearity range was 30.0-1.00 × 103 nmol/L (R2 >0.998) with the accuracy of 95.6%-107% and precision of ≤9% relative standard deviation (RSD). The applicability was also evaluated by N,N-dimethyl-carbamates with the LODs of 30.0 nmol/L for pirimicarb-exposed plasma based on dimethylcarbamyl nonapeptide. Because most of carbamate toxicants has methylcarbamyl or dimethylcarbamyl groups, this approach could be applied on the retrospective screening of carbamate toxicant exposure including CMNAs, carbamate pesticides or carbamate drugs. This study could provide an effective means in the fields of CWC verification, toxicological mechanism investigation and down-selection of potential treatment options.

Affordable Portable Platform for Classic Photometry and Low-Cost Determination of Cholinesterase Activity.

Excessive use of pesticides could potentially harm the environment for a long time. The reason for this is that the banned pesticide is still likely to be used incorrectly. Carbofuran and other banned pesticides that remain in the environment may also have a negative effect on human beings. In order to provide a better chance for effective environmental screening, this thesis describes a prototype of a photometer tested with cholinesterase to potentially detect pesticides in the environment. The open-source portable photodetection platform uses a color-programmable red, green and blue light-emitting diode (RGB LED) as a light source and a TSL230R light frequency sensor. Acetylcholinesterase from Electrophorus electricus (AChE) with high similarity to human AChE was used for biorecognition. The Ellman method was selected as a standard method. Two analytical approaches were applied: (1) subtraction of the output values after a certain period of time and (2) comparison of the slope values of the linear trend. The optimal preincubation time for carbofuran with AChE was 7 min. The limits of detection for carbofuran were 6.3 nmol/L for the kinetic assay and 13.5 nmol/L for the endpoint assay. The paper demonstrates that the open alternative for commercial photometry is equivalent. The concept based on the OS3P/OS3P could be used as a large-scale screening system.

Absorption, metabolism and distribution of carbosulfan in maize plants (Zea mays L.).

BACKGROUND: The insecticide carbosulfan is usually applied as a soil treatment or seed-coating agent, and so may be absorbed by crops and pose dietary risks. Understanding the uptake, metabolism and translocation of carbosulfan in crops is conducive to its safe application. In this study, we investigated the distribution of carbosulfan and its toxic metabolites in maize plants at both the tissue and subcellular levels, and explored the uptake and translocation mechanism of carbosulfan. RESULTS: Carbosulfan was mainly taken up by maize roots via the apoplast pathway, was preferentially distributed in cell walls (51.2%-57.0%) and most (85.0%) accumulated in roots with only weak upward translocation. Carbofuran, the main metabolite of carbosulfan in maize plants, was primarily stored in roots. However, carbofuran could be upwardly translocated to shoots and leaves because of its greater distribution in root-soluble components (24.4%-28.5%) compared with carbosulfan (9.7%-14.5%). This resulted from its greater solubility compared with its parent compound. The metabolite 3-hydroxycarbofuran was found in shoots and leaves. CONCLUSION: Carbosulfan could be passively absorbed by maize roots, mainly via the apoplastic pathway, and transformed into carbofuran and 3-hydroxycarbofuran. Although carbosulfan mostly accumulated in roots, its toxic metabolites carbofuran and 3-hydroxycarbofuran could be detected in shoots and leaves. This implies that there is a risk in the use of carbosulfan as a soil treatment or seed coating. © 2023 Society of Chemical Industry.

Near-infrared-excitable acetylcholinesterase-activated fluorescent probe for sensitive and anti-interference detection of pesticides in colored food.

The development of a common and anti-interference acetylcholinesterase (AChE) inhibition assay for plant-originated food samples has been of great challenge because of the prevalent and strong signal interferences from natural pigments. Plant pigments normally exhibit non-negligible absorbance in the UV-visible region. As a result, the signals of a typical near-infrared (NIR) fluorescent probe could be disturbed through primary inner filter effect if it is excited by UV-visible light during plant sample analysis. In this work, an NIR-excitable AChE-activated fluorescent probe was biomimetically designed and synthesized. And the NIR-excitation strategy was utilized for the anti-interference detection of organophosphate and carbamate pesticides in colored samples with this probe. Sensitive and rapid response to AChE and pesticides was achieved due to the high affinity of the biomimetic recognition unit in the probe. The limits of detection for four representative pesticides including dichlorvos, carbofuran, chlorpyrifos and methamidophos reached 0.0186 µg/L, 2.20 µg/L, 12.3 µg/L and 13.6 µg/L, respectively. Most importantly, fluorescent response to pesticide contents could be accurately measured in the coexistence of different plant pigments by this probe, and the measured results showed completely irrelevance to the plant pigments and their colors. Taking advantage of such probe, the new developed AChE inhibition assay showed good sensitivity and anti-interference ability in the detection of organophosphate and carbamate pesticides in real samples.

Heterogeneous distribution of carbofuran shaped by Pseudomonas stutzeri biofilms enhances biodegradation of agrochemicals.

Biodegradation, harnessing the metabolic versatility of microorganisms to reduce agrochemical contaminations, is commonly studied with enriched planktonic cells but overlooking the dominant lifestyle of microorganisms is to form biofilms, which compromises the efficiency of biodegradation in natural environment. Here, we employed a carbofuran-degrading bacterium Pseudomonas stutzeri PS21 to investigate how the bacterial biofilms formed and responded to agrochemicals. First, the PS21 biofilms formed with a core of bacterial cells enclosing with extracellular polymeric substances (EPSs), and the biofilms were active and resilient when exposed to carbofuran (up to 50 mg L-1). The formation was regulated by the second messenger bis-(3'-5')-cyclic di-guanosine monophosphate signaling, which strengthened the structural resistance and metabolic basis of biofilms to remain the degrading efficiency as comparable as the planktonic cells. Second, carbofuran distributed heterogeneously in the near-biofilm microenvironment via the covalent adsorption of biofilms, which provided a spontaneous force that enhanced the combination of carbofuran with biofilms to maintain high degrading activity. Additionally, we elucidated the biodegradation was driven by the integrated metabolic system of biofilms involving the extracellular enzymes located in the EPSs. This study exhibited the structural and metabolic advantages of microbial biofilms, highlighting the attractive potentials of exploring biofilm-based strategies to facilitate the in-situ bioremediation of organic contaminations.

Migration behavior and dietary exposure risk assessment of pesticides residues in honeysuckle (Lonicera japonica Thunb.) based on modified QuEChERS method coupled with tandem mass spectrometry.

The honeysuckle was widely appreciated as tea beverage owing to the biological activities and the unique aroma and flavor. It is in urgent requirement to explore the migration behavior and dietary exposure as the pesticide residues would bring about potential risks through honeysuckle intake. The optimized QuEChERS procedure coupled with the HPLC-MS/MS and GC-MS/MS methods were employed to determine 93 pesticide residues of seven classifications including carbamates, pyrethroid, triazoles, neonicotinoids, organophosphorus, organochlorine, and others for 93 honeysuckle samples from four primary production bases. As a result, 86.02% of the samples were contaminated by at least one pesticide. Unexpectedly, the banned pesticide of carbofuran was also identified. The migration behavior of metolcarb was the highest, whereas thiabendazole contributed less risk to the infusion with relative lower transfer rate. Both the chronic and acute exposure yielded low risk for human health with five high risk pesticides of dichlorvos, cyhalothrin, carbofuran, ethomyl, and pyridaben. Besides, this study provides foundation of dietary exposure risk assessment for honeysuckle and other likewise products.