Phenylboronic acid-functionalized magnetic metal-organic framework nanoparticles for magnetic solid phase extraction of five benzoylurea insecticides.

This research involves the construction of a phenylboronic acid-functionalized magnetic UiO-66 metal-organic framework (MOF) nanoparticle (CPBA@UiO-66@Fe3O4). Its design is primarily for the magnetic solid phase extraction (MSPE) of benzoylurea insecticides. An organic ligand, 2-amino terephthalic acid (2-ATPA), facilitated the introduction of amino groups while keeping the original crystal structure of UiO-66 intact. The constructed UiO-66 MOF showcases a porous structure and extensive surface area, thereby providing an optimal platform for further functionalization. The employment of 4-carboxylphenylboronic acid as a modifier notably amplified the extraction efficiency for benzoylureas. This improvement was due to the formation of B-N coordination and other secondary interactions. By integrating this with high-performance liquid chromatography (HPLC), we established a quantitative analytical method for benzoylurea insecticides. This method achieved a wide linear range (2.5-500 µg L-1 or 5-500 µg L-1), satisfactory recoveries (83.3-95.1%), and acceptable limits of detection (LODs: 0.3-1.0 µg L-1). The developed method proved successful when applied to six tea infusion samples, representing China's six major tea categories. Semi-fermented and light-fermented tea samples demonstrated relatively higher spiking recoveries.

Dual-mode detection of fluorine-containing pesticides (bifenthrin, flufenoxuron, diflubenzuron) via ratiometric fluorescence and the Tyndall Effect of fluorescent organic nanoparticles.

The Tyndall Effect assay (TEA) has been applied into colorimetric metal ion detection since 2019. However, the TEA-based sensor for pesticide detection has never been reported till now. Herein, a facile fluorescent organic nanoparticle (FON)-based sensor is firstly developed for fluorine-containing pesticide detection through ratiometric fluorescence assay (FLA) and TEA. For FLA, the intensity of the second-order Tyndall scattering peak (STS590nm) and the fluorescence peak of the FON-based sensor would increase and remain unchanged respectively when adding bifenthrin, flufenoxuron, and diflubenzuron. The detection limits were respectively 9.34, 6.91, and 3.60 µg/kg. For TEA, the increased STS590nm intensity displayed a bright and visible light beam. An economical, simple, and portable device was then constructed to visually monitor the analytes. The sensor was successfully used to detect the analytes in teas through FLA and TEA with the recoveries and RSD ranging from 86.27-100.00 %, and 0.00-5.68 %, respectively.

Concentration and risk assessment of PCNs in green tea in different locations in China.

Polychlorinated naphthalenes (PCNs) were added to the Stockholm Convention list of persistent organic pollutants in 2015. PCNs are mainly unintentionally produced during industrial processes nowadays, and can be widely found in environmental media and foodstuffs. Dietary intake is the primary pathway for human exposure to PCNs. PCNs in different categories of foodstuffs have been reported. However, little information on PCN concentrations in green tea, a popular beverage worldwide is available. In this study, all 75 PCN congener concentrations and distributions in green tea samples (n = 102) from 11 regions in China were determined, and risk assessment of human exposure to PCNs through tea consumption was conducted. The PCN concentrations in all the green tea samples were 3.62-175 pg/g dry weight (mean 36.1 pg/g dry weight). Similar PCN homolog and congener profiles were found in green tea samples from different areas. The dominant PCN homologs in all of the green tea samples were di-CNs, tetra-CNs, and tri-CNs. No direct relationships were found between PCN emission sources and PCN concentrations in the green tea samples. The brewing technique could affect the PCN concentrations and homolog profiles in tea leaves. PCNs in green tea from China were found to pose little risk to humans.

Short- and medium-chain chlorinated paraffins in green tea from 11 Chinese provinces and their migration from packaging.

Chlorinated paraffins (CPs) have been found to occur ubiquitously in foodstuff of both animal and plant origin. However, limited information is available on the content of CPs in green tea, one of the most commonly consumed beverages worldwide. Herein, 107 commercial green tea samples originating from 11 provinces of China, were collected to study the occurrence of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively). The concentration of SCCPs in all green tea samples ranged from 4.99 to 717 ng/g (mean: 55.7 ng/g), while MCCPs ranged from 2.55 to 543 ng/g (mean: 33.5 ng/g). CP profiles in green tea samples from different provinces exhibited no regional differences. To identify the potential sources of CPs in green tea, 19 tea packaging samples were collected and analyzed, showing that SCCPs and MCCPs existed at much higher concentrations in the tea packaging material than in the teas. Migration tests indicated that CPs could migrate from packaging into teas during storage, with the migration velocity and efficiency of SCCPs being higher than MCCPs.

A facile and total water-soluble fluorescent organic nanoparticles-based sensor for Hg2+ detection and its application in tea samples.

In this study, a novel FONs-based sensor P-M(w) was synthesized using 1-Pyrenecarboxaldehyde and L-methionine through facile hydrothermal strategy. The fluorescence emission peaks of the acquired P-M(w) would show specific changes after the addition of Hg2+ due to interfering the PET process and inducing nano-structure conformational rigidification of P-M(w). Notably, the water-soluble FONs-based sensor was firstly used to detect Hg2+ in tea samples providing a new material choice for the fluorescence sensor construction of metal ion detection. Besides, the qualitative and quantitative analysis of Hg2+ could be carried out with P-M (w) at a very low concentration (1 µg/mL) meaning that the acquired P-M(w) synthesized by few grams of reactants may satisfy the detection of approximate fifty thousand samples.

1-Octyl-3-methylimidazolium hexafluorophosphate-functionalised magnetic poly ß-cyclodextrin for magnetic solid-phase extraction ofpyrethroids from tea infusions.

In this study, a novel sorbent, 1-octyl-3-methylimidazolium hexafluorophosphate functionalised magnetic poly ß-cyclodextrin, was successfully synthesised and applied to magnetic solid-phase extraction for the determination of pyrethroids in tea infusions. The sorbent was characterised by transmission electron microscopy, energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, vibrating sample magnetometer and Brunauer-Emmett-Teller measurement. All factors affecting extraction efficiency, such as sorbent amount, extraction time, ionic strength and desorption conditions, were optimised individually. Under the chosen conditions, wide linearity (2.5-500 µg L-1) with determination coefficients ranging from 0.9995 to 0.9999, low limits of detection of 0.32-0.54 µg L-1 and good precision (intra-day: 2.6-7.0%; inter-day: 3.5-7.6%) were achieved for four pyrethroids in tea infusions. The relative recoveries of target analytes in real tea infusion samples were from 70% to 101% with relative standard deviations lower than 9.1%. We conclude that the proposed method is promising in the detection of pyrethroids in tea infusions.

Use of 1-octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine as sorbent for the extraction of pyrethroid insecticides from tea infusion.

Magnetic hyperbranched polyamideamine was carboxylated using succinic anhydride and modified further with 1-octyl-3-methylimidazole hexafluorophosphate successively. The morphology and chemical composition of the prepared material was characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller measurement, X-ray photoelectron spectroscopy, etc. 1-Octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine was used as sorbent in the magnetic solid-phase extraction for the separation and enrichment of five pyrethroid insecticides from tea infusion. The magnetic solid-phase extraction method proposed in this article has low method detection limits (0.53-0.71 ng/mL), acceptable coefficient of determination (0.9992-0.9998), wide linear ranges (2.5-500.0 ng/mL), and good repeatability (intraday: 1.2-6.3%; interday: 1.6-5.4%). In the detection of five pyrethroid insecticides in tea infusion, relative recoveries were in the range from 87.7 to 114.7% with satisfactory relative standard deviations (0.2-7.4%). With the aid of quantum chemistry calculations, the interaction energy between the sorbent and five pyrethroid insecticides was calculated, which proved the necessity of the modification of 1-octyl-3-methylimidazole hexafluorophosphate.

Hydrophobic deep eutectic solvents based membrane emulsification-assisted liquid-phase microextraction method for determination of pyrethroids in tea beverages.

Deep eutectic solvents (DESs) were used as an extractant for the determination of pyrethroids in environmental water and tea beverage samples. Three different acids were chosen as hydrogen bond donors for preparation of DESs, and decanoic acid was optimal because of its high recovery. Factors affecting relative recovery were optimized individually, including salt addition, surfactant addition, extraction temperature, DES amount, and sample volume etc. Under the optimized experimental conditions, the relative recovery of pyrethroids was from 89.3% to 97.7%, with relative standard deviation (RSD) values ranging from 1.75% to 2.73%. The linear correlation coefficient ranged from 0.9981 to 0.9992, and the linear range was between 1.9 and 500 µg/L. Based on a signal-to-noise ratio (S/N) of 3:1, the limit of detection (LOD) values were 0.56 to 1.24 µg/L. The enrichment factor ranged from 92 to 105. In conclusion, good extraction efficiency was achieved in tea beverage samples under the optimized conditions.

Attapulgite modified magnetic metal-organic frameworks for magnetic solid phase extraction and determinations of benzoylurea insecticides in tea infusions.

Herein, we developed a novel magnetic solid phase extraction method based on attapulgite-modified magnetic metal-organic frameworks (ATP@Fe3O4@ZIF-8), and this method could be used for the determination of benzoylureas when it was coupled with high-performance liquid chromatography. The established method was validated in terms of linearity (2.5-500 µg L-1, with correlation coefficient (R2) > 0.9994), accuracy (with satisfactory recovery of 88.29-95.99%) and precision (with relative standard deviation (RSD) of less than 8%). In addition, the enrichment factors (EF) ranged from 63.6 to 72.2. Limit of detection (LOD) and limit of quantitation (LOQ) were 0.7-3.2 µg L-1 and 2.3-10.7 µg L-1, respectively. Moreover, there was hardly any noticeable loss of the extraction efficiency when this extraction method undergoes five cycles. Finally, this method was successfully used for the determination of six benzoylureas in different tea infusions and the determined relative recoveries ranged from 78.8 to 114.3%.

Extraction of benzoylurea pesticides from tea and fruit juices using deep eutectic solvents.

In this study, low-density deep eutectic solvent combined with dispersive liquid-liquid microextraction was applied to the extraction of five benzoylurea insecticides (BUs, including diflubenzuron, triflumuron, hexaflumuron, flufenoxuron, and chlorfluazuron) from beverages. Then the extracted and concentrated samples were analyzed and detected using the high-performance liquid chromatography combined with an ultraviolet detector. The DESs were synthesized by [P14,6,6,6]Cl as hydrogen bond acceptor and tetradecyl alcohol as hydrogen bond donor, and then characterized by Fourier transform infrared spectroscopy. In the experiment, the key factors affecting the extraction efficiency were screened by Plackett-Burman design and optimized with the central composite design. The extraction recovery rates were 85.91-95.12%. The limits of detection and correlation coefficients of the method were 0.30-0.60 µg L-1 and 0.9992-0.9997. Finally, the method was applied to determine the BUs in four beverage samples, and satisfactory recoveries, within the range of 76.87-101.19% were achieved. The present method has the potential to be applied to the detection of BUs in aqueous samples.

Humic acid functionalized hyperbranched polytriazine based dispersive solid-phase extraction for acaricides determination in tea matrix.

Hyperbranched polytriazine functionalized with humic acid was prepared and developed as new sorbents for dispersive solid-phase extraction of three acaricides (clofentezine, fenpyroximate, and pyridaben) in tea samples combined with high-performance liquid chromatography detection. The sorbents were characterized by scanning electron microscopy, energy dispersive spectroscopy, Zeta-potential, and Fourier transform infrared spectroscopy. The extraction parameters (extraction time, ionic strength, desorption conditions) were optimized. The adsorption mechanism was evaluated utilizing Fourier transform infrared spectra. Under optimum conditions, satisfactory analytical performances were achieved, which included high precision (1.33-9.62%), low limits of detection (0.19-3.54 µg/L), and wide linear range (2.5-500 µg/L) for the analysis of the acaricides. Moreover, the proposed method proved highly effective for the determination of acaricides in tea samples, with the relative recoveries in the range of 65.20-108.13% and relative standard deviations < 9.87%. The method has great application potential for the detection of acaricides in tea samples.

Magnetic solid-phase extraction of benzoylurea insecticides in tea samples with Fe3 O4 -hyperbranched polyester magnetic composite as sorbent.

In this work, a method for the analysis of benzoylurea insecticides, including hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron, in tea samples by high-performance liquid chromatography with Fe3 O4 -hyperbranched polyester nanocomposite as the adsorbent for magnetic solid-phase extraction was developed. The magnetic nanocomposite was prepared and characterized by infrared spectroscopy, vibrating sample magnetometry, and scanning electron microscopy. The as-prepared nanocomposite was used as a sorbent for the extraction and preconcentration of pesticide residues in tea samples. The extraction and desorption conditions, including mass ratios of raw materials, amount of sorbent, pH value, extraction time, and desorption time, were investigated. Under the final conditions chosen for the analysis, good linearity was obtained for all the tested compounds, with R2 values of at least 0.9979. The limits of detection were determined in the range of 0.15-0.3 µg/L. The recovery obtained from the analysis of tea samples with various spiked concentrations was between 90.7 and 98.4%, with relative standard deviations (n = 4) lower than 4.1%. Furthermore, the present approach was successfully applied to the quantitative determination of residues of benzoylurea insecticides in real samples.

Vortex-assisted deep eutectic solvent reversed-phase liquid-liquid microextraction of triazine herbicides in edible vegetable oils.

In this study, four triazine herbicides-namely, simazine, ametryn, prometryn and terbuthylazine-were separated and determined using high-performance liquid chromatography coupled with ultraviolet detector (HPLC-UVD). The deep eutectic solvent (DES) formed by tetrabutylammonium chloride ([N4444]Cl, TBA) and ethylene glycol (EG) was selected as the extraction solvent of vortex-assisted reversed-phase liquid-liquid microextraction (VA-RPLLME). The application of the hydrophilic DES expands the range of choice for LLME. The experimental parameters affecting the extraction recoveries, including the amount of the DES, the sample volume and the vortex time, were investigated and optimized by the design of experiments (DoE) methodology. A quadratic model, namely central composite face-centered (CCF) design featuring 20 runs was used instead of the conventional trial and error approach. Under optimum conditions, the limits of determination (LODs) of the method were 0.60-1.50 µg L-1. The enrichment factors for the analytes ranged from 27 to 31. The extraction recoveries were in the range of 84.1-104.9%, and the intra-day, inter-day and intermediate relative standard deviations (RSDs) were less than 8.4%. Finally, the method was applied for the determination of triazine herbicides in vegetable oil samples. The obtained recoveries were in the range of 60.1-107.2% and RSDs were lower than 8.1%. In general, VA-RPLLME can be complementary to the present available methods for the determination of triazine herbicides in vegetable oil samples.

Ionic liquid-type surfactant modified attapulgite as a novel and efficient dispersive solid phase material for fast determination of pyrethroids in tea drinks.

In this study, a novel ionic liquid-type surfactant modified attapulgite named as 1-dodecyl-3-methylimidazolium bromide-attapulgite (C12MIM-ATP) is successfully prepared and applied in dispersive solid phase extraction (dSPE) for the fast determination of pyrethroid residues in tea drinks. The primary factors that influenced the extraction efficiency, including sorbent type, amount of sorbent, extraction time, desorption conditions, pH and ionic strength, are investigated. The optimized results reveal that the extraction and desorption equilibria are rapidly obtained within 1 min. Under the optimized conditions, good linearity (2-500 µg/L) is observed for four pyrethroids in tea drinks with determination coefficients (r2) ranged from 0.9992 to 1.0000. The limits of detection (LODs) are 0.6 µg/L for all pesticides. Acceptable extraction recoveries of target analytes are found from 90.28 to 107.56% with relative standard deviations (RSDs) less than 8.30% in real tea drink samples. The batch-to-bath repeatability is evaluated by recovery test on five independent synthesized C12MIM-ATP sorbents. Satisfactory batch-to-batch repeatability is obtained with the recovery factors varied in 15%. A small matrix effect is observed using C12MIM-ATP as the sorbent for detection pyrethroids in tea drinks.

Rapid analysis of fungicides in tea infusions using ionic liquid immobilized fabric phase sorptive extraction with the assistance of surfactant fungicides analysis using IL-FPSE assisted with surfactant.

A green, simple, inexpensive, and sensitive ionic liquid immobilized fabric phase sorptive extraction method coupled with high performance liquid chromatography was developed for rapid screening and simultaneous determination of four fungicides (azoxystrobin, chlorothalonil, cyprodinil and trifloxystrobin) residues in tea infusions. This IL modified extraction fiber is capable of extracting target analytes directly from complicated tea water matrices with the addition of surfactant. A series of extraction conditions were investigated by one-factor-at-a-time approach and orthogonal test. After a series experiments, the optimum conditions were found to be 10% [HIMIM]NTf2 as coating solution, 2min vortex time, 500µL acetonitrile as dispersive solvent and 2min desorption time. Under the above conditions, the proposed technique was applied to detect fungicides from real tea water samples with satisfactory results.

In-syringe dispersive liquid-liquid microextraction based on the solidification of ionic liquids for the determination of benzoylurea insecticides in water and tea beverage samples.

A novel in-syringe dispersive liquid-liquid microextraction based on the solidification of ionic liquids (in-syringe SIL-DLLME) was coupled with high-performance liquid chromatography-ultraviolet detector (HPLC-UVD) to detect five benzoylurea insecticides (BUs) in water and tea beverage samples. In this method, the hydrophobic ionic liquid [N8881][PF6] was formed in situ by the metathesis reaction between [N8881]Cl and the anion-exchange reagent KPF6 to extract the target analytes. The whole extraction procedure was performed in a syringe. The solidified extractant could be separated from the aqueous phase by exposing the emulsified extraction solution to an ice bath and then easily collected by squeezing out the aqueous phase through the prepared NWPP-based needle. Various parameters affecting the extraction efficiency, such as the amount of [N8881]Cl, the molar ratio of [N8881]Cl to KPF6, salt addition, cooling time, solution temperature, sample pH and sample volume, were evaluated. Under the optimized conditions, the proposed method was validated with satisfactory results: good linearities with coefficients of determination greater than 0.99 were obtained in the range of 2-500µgL-1; the limits of detection varied between 0.29 and 0.59µgL-1; the recoveries of the five benzoylurea insecticides ranged from 85.93% to 90.52%; and the intra-day (n=3) and inter-day (n=3) relative standard deviations were less than 5.36%. Finally, the proposed method was successfully used for the determination of BUs in real water and tea beverage samples.

Using ß-cyclodextrin/attapulgite-immobilized ionic liquid as sorbent in dispersive solid-phase microextraction to detect the benzoylurea insecticide contents of honey and tea beverages.

A green, simple, inexpensive dispersive solid-phase microextraction method coupled with high-performance liquid chromatography was developed for rapid screening and selective recognition of benzoylurea insecticides (BUs) in honey and tea beverages. A novel adsorbent, ionic liquid (IL)-modified ß-cyclodextrin/attapulgite (ß-CD/ATP), was prepared by immobilizing IL on the surface of ß-CD/ATP. A series of demanding extraction conditions were investigated through the experimental design. Under optimum conditions, the limits of detection for the analytes varied from 0.12 to 0.21 µg L(-1). The enrichment factors ranged from 112 to 150 folds. Linearities in the range of 5-500 ng m L(-1) were achieved for four BUs, while the correlation coefficients ranged from 0.9997 to 1.0000 and the recoveries from 84.5% to 104.7%. The precision of this method for the four BUs corresponded to intra-day and inter-day RSDs% lower than 3.85%. Finally, the proposed technique was applied for the preconcentration of the BUs from real samples with satisfactory results.