•Rapid one-step cleanup method to minimize matrix effects for pesticides in tea.•Removal of caffeine and polyphenols were achieved by PCX-based DSPE procedure.•Weak absolute matrix effect and low ...relative matrix effect were achieved.•LC–HRMS with pre-column dilution injection was used to overcome solvent effects.•This method was validated and applied to the alkaline pesticides analysis in tea.
Matrix effects in complex tea matrices remains a great challenge to rapid quantitative analysis of multi-residue pesticides by analysis of mass spectrometry. Herein, a mixed-mode polymer cationic exchange based dispersive solid-phase extraction (DSPE) procedure was established to eliminate matrix effects of tea for a rapid target alkaline multi-residue pesticides analysis. One-step DSPE procedure can eliminate matrix interferences from the tea extract without additional dilution or tedious cleanup operations. Liquid chromatography–high resolution mass spectrometry using pre-column dilution injection mode was used as the detection technique, while eliminating solvent effects of target analytes and improving the detection sensitivity. Based on this effective analytical method, the results of absolute matrix effects were within 0.77–1.08 for quantitation of the 68 alkaline pesticides, and superior relative matrix effects were also achieved with RSD values below 9.8%. Finally, this method was validated and applied to the alkaline pesticides analysis of the 123 tea samples.
•g-C3N4, Bi2WO6 & g-C3N4/Bi2WO6 nanocomposites are synthesized and grafted on PVDF membrane.•Surface energy has increased by 60.2% in g-C3N4/Bi2WO6 nanocomposites membrane than neat ...membrane.•g-C3N4/Bi2WO6 PVDF membrane has shown 80% photodegradation of pirimicarb at pH 5.
Pirimicarb, a commercially used insecticide, contains carbamate, which affects the nervous system of insects and living organisms, thus inhibiting their growth and increasing the production of crops. However, it has an impact on the ecosystem of groundwater by permeating the soil profile.
The g-C3N4, Bi2WO6 & g-C3N4/Bi2WO6 nanocomposites were synthesized by hydrothermal method and grafted on the PVDF membranes via in-situ polymerization. The pirimicarb wastewater of different pH 5,7 & 9 was synthetically prepared, and the performance of the membrane was tested to study the reduction and photodegradation of as-prepared pirimicarb wastewater.
The surface energy had increased from 88.65 to 145.1 mJ/m2, g-C3N4/ Bi2WO6 nanocomposites on the PVDF membranes. The water contact angle of the membrane ranges from 57.9° to 37.7°, indicating that the membranes have higher hydrophilic characteristics. The water permanence is in the decreasing order of M1 (PAA/PVDF)> M6 (0.5wt% g-C3N4/Bi2WO6/PAA/PVDF)> M3 (1wt% Bi2WO6/PAA/PVDF)> M7 (1wt% g-C3N4/Bi2WO6/PAA/PVDF)> M4 (0.5wt% g-C3N4/PAA/PVDF)> M2 (0.5wt% Bi2WO6/PAA/PVDF)> M5 (1wt% g-C3N4/PAA/PVDF)> Neat (PVDF). The photodegradation studies stated that upon adding nanocomposites such as g-C3N4/Bi2WO6, the membranes undergo degradation of 80% at pH 5, which is higher than the PVDF/PAA (M1) membrane.
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•Enzymeless voltammetric sensor for determination of pirimicarb is presented.•Eco-Friendly, high-performance pirimicarb sensor using AuNPs@GO/IL@SPCE was accomplished.•The oxidation ...mechanism of pirimicarb was illustrated using an experimental-theoretical methodology.•Quantification of pirimicarb in groundwater and surface water samples was demonstrated.
Carbamate pesticide residue assessments are important for water and environmental quality. An eco-friendly electrochemical sensor for direct determination of pirimicarb (PMC) based on graphene oxide (GO) and Ionic liquid (IL) composites decorated with gold nanoparticles has been developed. The resulting AuNPs@GO/IL@SPCE sensor was characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analysis. The electrode’s electrochemical characteristics were evaluated using cyclic voltammetry and electrochemical impedance spectroscopy. The impact of different modifier materials on the sensor performance and its stability was investigated systematically using a combination of experimental and theoretical studies. Under optimal conditions, the AuNPs@GO/IL@SPCE is used for sensitive detection of PMC in a concentration range from 50–1500 µM with a detection limit of 4.49 µM. Furthermore, the sensor exhibits excellent selectivity towards tested interfering species, reproducibility, and stability. Finally, the PMC detection in groundwater and surface water was achieved using the developed sensor with a 97.38 − 103.36 % recovery.
•A fluorescent sensor based on S-CQDs was constructed to detect pirimicarb.•A green deep eutectic solvent was synthesized to extract pirimicarb.•S-CQDs had vast negative charges as the fluorescence ...probe.•Electrostatic interactions led to fluorescence quenching of S-CQDs.•The proposed extraction and detection strategy has prospects in food analysis.
A novel deep eutectic solvent-based extraction and sulfur-doped carbon quantum dots (S-CQDs) serving as fluorescence probes to detect pirimicarb in cereals were established. The deep eutectic solvent was synthesized using choline chloride and butanediol, achieving direct and efficient extraction of pirimicarb residue in the cereals. The fluorescence quenching of S-CQDs was caused by the electrostatic interaction between the negatively charged S-CQDs and positively charged thiocholine, which was the hydrolysate of acetylthiocholine. The fluorescence of S-CQDs was enhanced as the activity of acetylcholinesterase (AChE) was inhibited by pirimicarb, achieving the detection of pirimicarb in the cereal samples. The limit of detection (LOD) was 0.006 μg mL−1. The recovery ranged from 96.6% to 108.2%. This extraction and detection method of pirimicarb based on an environmentally friendly DES and S-CQD fluorescent sensor maintains good stability and convenience, offering a promising strategy for extracting and testing harmful substances in food samples.
The following statement explaining the meaning of the sign (†) behind the co-first author names should be included either in the area on the left of the research paper currently stating the citation, ...corresponding author etc., or underneath the author affiliations, and declaring the following: “†These authors have contributed equally to this work and share first authorship.” The authors apologize for this error and state that this does not change the scientific conclusions of the article in any way. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher. www.frontiersin.orgThessa Van Limbergen1,2† www.frontiersin.orgInez Henriette Roegiers3† www.frontiersin.orgRobin Bonné2,4 www.frontiersin.orgFederica Mare1 www.frontiersin.orgTom Haeldermans5 www.frontiersin.orgBjorn Joos6,7,8 www.frontiersin.orgOlivier Nouwen1 www.frontiersin.orgJean V. Manca2 www.frontiersin.orgJaco Vangronsveld1,9 www.frontiersin.orgSofie Thijs1* * 1Department of Biology, Environmental Microbiology, Centre for Environmental Sciences, Faculty of Sciences, Hasselt University, Diepenbeek, Belgium * 2X-LAB, Department of Physics, Faculty of Sciences, Hasselt University, Diepenbeek, Belgium * 3Center for Microbial Ecology and Technology, Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium * 4Department of Bioscience, Center for Electromicrobiology, Aarhus University, Aarhus, Denmark * 5Research Group of Analytical and Applied Chemistry, IMO, Hasselt University, Diepenbeek, Belgium * 6Institute for Materials Research (imo-imomec), DESINe Team, Hasselt University, Diepenbeek, Belgium * 7Imec, Division Imomec, Diepenbeek, Belgium * 8EnergyVille, Genk, Belgium * 9Department of Plant Physiology and Biophysics, Institute of Biological Science, Maria Curie-Skłodowska University, Lublin, Poland
Pirimicarb as a pesticide is used to control the aphids in the agriculture field; however, it affects the groundwater ecosystem by leaching through the soil profile. The post-synthetic amine and BWO ...modified MIL-100 (Fe) nanofillers were synthesized. The photocatalytic property of amine-functionalized and BWO@MIL-100(Fe) nanofillers was confirmed by the lesser bandgap energy than the unmodified MIL-100 (Fe) nanofiller. Herein, we constructed a nanofillers grafted PVDF membrane via in-situ polymerization technique for the pirimicarb reduction and photodegradation. Furthermore, the nanofiller's grafted membranes were characterized by FESEM, XRD, FTIR, and contact angle analysis. The carboxylic acid peak was observed on the FTIR which demonstrated the PAA grafted on the membrane surface and similar crystalline peaks evident that the nanofillers were grafted on the membrane surface. Furthermore, surface morphology studies have exhibited the dispersion of nanofillers and enhanced microvoids in the cross-section of the membrane. The decrease in the water contact angle of the membrane depicted the improved antifouling properties and surface energy. The nanofiller's grafted membranes have shown higher hydrophilicity correlated well with the enhanced pure water flux in the order M4 > M5 > M2 > M3 > M6 > M7 compared to the neat membrane (M1). In BWO@MIL-100(Fe) membrane has shown a higher permeate flux (25.99 L m−2.h−1) than the neat PVDF membrane. The BWO@MIL-100(Fe) grafted PVDF membrane has also shown excellent pirimicarb photodegradation of 81% at pH 5. The proposed MIL-100 (Fe) and bismuth tungsten nanocomposite will pave the way for the different MOF-based photocatalytic materials for membrane-based pesticide degradation.
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•NH2 and BWO modified MIL-100(Fe) nanofillers were synthesized by solvothermal method.•Nanofillers were grafted on the PVDF membrane via In-situ polymerization.•BWO@MIL-100(Fe) membrane has shown permeate flux (25.99 L m−2.h−1) and rejection of 84%.•The BWO@MIL-100(Fe) grafted membrane has shown 81% of pirimicarb degradation.
A novel green pH-sensitive fluorescent probe based on the surface passivation was designed for sensitive, rapid and reliable detection of pirimicarb (PRC). Using natural deep eutectic solvent (NADES) ...as the green precursor, N-CDs were hydrothermally synthesized, and combined with rhodamine B (RhB) to display strong fluorescence emission peaks at 400 and 582 nm, respectively. Upon the addition of PRC, the fluorescence sensor resulted in the enhanced fluorescence at 400 nm, while the orange signals hardly changed. Moreover, under the optimal conditions, the proposed assay exhibited super-fast, high selectivity and sensitivity for PRC with a wide linear range from 0.5 to 200 μg mL−1 and the relatively low detection limit around 0.3 μg mL−1. Importantly, real sample analyses demonstrated that the as-presented sensor had excellent potential in pesticide monitoring. Meanwhile, the enhanced photoluminescence that become emissive upon stability from N-CDs was attributed to the reduction of surface defects after the surface passivation. In virtue of superior biocompatibility, excellent optical properties and low toxicity, the N-CDs were further employed to monitor the pH value.
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•A novel ratio fluorescence sensor have been developed to identify pirimicarb and pH.•Using deep eutectic solvent from dl-malic acid and glycerol as green precursor.•Exhibiting good selectivity and sensitivity to pirimicarb with ultra-fast response time.•Sensor avoids the influences caused by probe concentration and drifts of incident light system.•N-CDs/RhB nanohybrid was a promising candidate for ratiometric sensing.
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•Photocatalytic oxidation of pirimicarb in water was studied.•The study was performed using ZnO–TiO2 systems under artificial irradiation.•ZnO and TiO2 enhanced photodegradation in ...comparison with Zn2TiO4 and ZnTiO3.•Pirimicarb was totally degraded using ZnO and TiO2.•5 intermediates were identified and a mechanism of degradation has been proposed.
The photocatalytic degradation of pirimicarb in pure water has been studied using zinc oxide (ZnO), titanium dioxide (TiO2) and zinc titanates (Zn2TiO4 and ZnTiO3) under artificial light (300–460nm) irradiation. Comparison of catalysts showed that TiO2 is the most efficient for the removal of pirimicarb and their transformation products. To obtain a better understanding of the mechanistic details of these ZnO–TiO2-assisted photodegradation of pirimicarb, the transformation products of the processes were identified by liquid chromatography tandem mass spectrometry (LC-MS2) and liquid chromatography time of flight mass spectrometry (LC-TOF/MS) techniques. The probable photodegradation pathways are proposed and discussed. The main steps involved: N-dealkylation of the 2-dimethylamino group to form the carbamate and decarbamoylation of the carbamate moiety with further N-dealkylation of the 2-dimethylamino group to have the hydroxypyrimidines.
Pyrene-appended β-cyclodextrin based multi-responsive self-assembled nanoaggregates allowed guest specific distinctive detection of pirimicarb, TNT, TNB and picric acid.
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•A ...pyrene-appended cyclodextrin probe was synthesized in a highly efficient manner.•The fluorescent probe self-assembles into nanoaggregates in water.•The nanoaggregates are stimuli-responsive.•The nanoaggregates show guest specific distinctive detection of pirimicarb and trinitro-explosives.
Multi-responsive fluorescent aggregates have attracted growing interest for the development of high-performance sensory materials for monitoring environmental hazards. Herein, we develop a multi-responsive pyrene-appended β-cyclodextrin probe 25, which self-assembles into nanoaggregates (150 nm–164 nm) in water driven by hydrophobic π–π interactions, evaluated by Tyndall scattering, dynamic light scattering (DLS), and transmission electron microscopy (TEM). The formed fluorescent nanoaggregates were found to exhibit an efficient and selective ratiometric detection of pirimicarb (PC), a potent toxic carbamate pesticide with significant enhancement (85 times) in the monomer to excimer ratio (IM/IE). Further, among the trinitroaromatic explosives, the formed nanoaggregates displayed discriminative fluorogenic detection of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB) and picric acid (PA). Significant reduction in the size and morphological changes in the shape of the nanoaggregates were observed upon interaction with 50 and 100 equivalents of PC, TNT, TNB and PA. The highly ordered intermolecular packing of pyrene moieties in the nanoaggregates and their orientation specific monomer (IM) and excimer (IE) emissions allowed guest specific distinctive detection of PC, TNT, TNB and PA, which otherwise, have not been achieved so far.
A sensitive and readily deployable analytical method has been reported for the simultaneous analysis of pirimicarb (PRM) and fenitrothion (FEN) pesticide residues in environmental water samples using ...fabric phase sorptive extraction (FPSE) followed by high-performance liquid chromatography combined with photodiode array (HPLC-PDA) detector. Both pesticides were successfully determined with a Luna omega C18 column under isocratic elution mode by means of acetonitrile and phosphate buffer (pH 3.0) as the mobile phase. The quantitative data for PRM and FEN were obtained at their maximum wavelengths of 310 nm and 268 nm, respectively. The calibration plots were linear in the range 10.00–750.00 ng mL
−1
and 10.00–900.00 ng mL
−1
with correlation coefficient of 0.9984 and 0.9992 for PRM and FEN, respectively. Major FPSE experimental variables were investigated in detail, such as contact time with the FPSE membrane, pH and electrolyte concentration, and the volume and type of desorption solvent. Under the optimized conditions, the developed method showed satisfactory reproducibility with relative standard deviations less than 2.5% and low limits of detection of 2.98 and 3.02 ng mL
−1
for PRM and FEN, respectively. The combined procedure allows for enhancement factors ranging from 88 to 113, with pre-concentration values of 125 for both analytes. The chromatographic resolutions were approx. 12 for FEN (retention factor of 3.52) and PRM (retention factor of 6.09), respectively, with a selectivity factor of 1.73. Finally, the validated method was successfully applied to real environmental water samples for the determination of these pesticides.
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