[Determination of five veterinary drug residues in milk by ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitrap mass spectrometry based on modified chitosan membrane purification].

Milk is an important consumer product with high nutritional value. The presence of veterinary drug residues in milk owing to the indiscriminate use of veterinary drugs may affect consumer health. In the mass spectrometric analysis of trace compounds, chromatographic co-eluting components easily interfere with the mass spectral signals obtained, affecting the accuracy of qualitative and quantitative analyses. Matrix purification is a promising method to reduce the matrix effect. Chitosan is a natural biopolymer with numerous active functional groups such as amino, acetyl, and hydroxyl groups; these groups can adsorb lipids through hydrophobic and electrostatic interactions. Chitosan also has the advantages of low production cost, stable chemical properties, and convenient modification. Novel chitosan-based materials are promising candidates for lipid purification. In this study, a chitosan membrane was modified with trimethoxyoctadecylsilane (C18-CSM). C18-CSM was prepared through one-step hydrolysis and used as a dispersive solid phase extraction (DSPE) adsorbent to purify the matrix during milk pretreatment. We combined C18-CSM with ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitrap mass spectrometry (UHPLC-Q/Exactive Orbitrap MS) to develop an effective method for the extraction and determination of ofloxacin, enrofloxacin, ciprofloxacin, diazepam, and metronidazole in milk. C18-CSM was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and water contact angle testing. The results indicated that the material has a rough surface and uniformly dense cross-section. The water contact angle of C18-CSM was 104°, indicating its good hydrophobicity. The pretreatment conditions (extraction solvent, dosage of NaCl, extraction frequency, and dosage of C18-CSM) that influenced the recoveries of the five veterinary drugs were investigated in detail. The optimal conditions were established as follows: 5% formic acid in acetonitrile, 1 g NaCl, extraction 1 time, 20 mg C18-CSM. Separation was performed on a Hypersil GOLD VANQUISH column (100 mm×2.1 mm, 1.9 µm). The mobile phase consisted of 0.1% formic acid aqueous solution and 0.1% formic acid in acetonitrile, and was flowed at a rate of 0.3 mL/min. The sample injection volume was 1 µL, and the column temperature was maintained at 25 ℃. Mass spectrometric analysis was performed in positive electrospray ionization mode. To verify the necessity of the purification material, the matrix effect was investigated using the matrix-matched standard curve method. The use of C18-CSM reduced the matrix effects of the five necessity drugs from the range of -22%-8.8% to the range of -13%-3.6%, indicating that C18-CSM is a highly efficient DSPE material. Under optimal conditions, the developed method showed good linearities within the range of 0.5-100 µg/L, with correlation coefficients (r2)≥0.9970. The limits of detection(LODs) and quantification (LOQs) were 0.2 µg/L and 0.5 µg/L, respectively. To assess the accuracy and precision of the method, we prepared milk samples with three spiked levels (low, medium, and high). The recoveries of the five veterinary drugs were ranged from 79.5% to 115%, and the intra-day and inter-day relative standard deviations were 7.0%-13% (n=6) and 1.3%-11% (n=3), respectively. This study provides a simple, accurate, and reliable method for the rapid and simultaneous determination of the five veterinary drug residues in milk.

Fast Determination of Eleven Food Additives in River Water Using C18 Functionalized Magnetic Organic Polymer Nanocomposite Followed by High-Performance Liquid Chromatography.

A novel magnetic nanomaterial with Fe3O4 as the core, PS-DVB as the shell layer, and the surface modified with C18 (C18-PS-DVB-Fe3O4) had been synthesized by seeded emulsion polymerization. C18-PS-DVB-Fe3O4 retains the advantages of the chemical stability, large porosity, and uniform morphology of organic polymers and has the magnetic properties of Fe3O4. A simple, flexible, and efficient magnetic dispersive solid phase extraction (Mag-dSPE) method for the extraction of preservatives, sweeteners, and colorants in river water was established. C18-PS-DVB-Fe3O4 was used as an adsorbent for Mag-dSPE and was coupled with high-performance liquid chromatography (HPLC) to detect 11 food additives: acesulfame, amaranth, benzoic acid, tartrazine, saccharin sodium, sorbic acid, dehydroacetic acid, sunset yellow, allura red, brilliant blue, and erythrosine. Under the optimum extraction conditions, combined with ChromCoreTMAQC18 (5 µm, 4.6 × 250 mm), 20 mmol/L ammonium acetate aqueous solution and methanol were used as mobile phases, and the detection wavelengths were 240 nm and 410 nm. The limits of detection (LODs) of 11 food additives were 0.6-3.1 µg/L with satisfactory recoveries ranging from 86.53% to 106.32%. And the material could be reused for five cycles without much sacrifice of extraction efficiency. The proposed method has been used to determine food additives in river water samples, and results demonstrate the applicability of the proposed C18-PS-DVB-Fe3O4 Mag-dSPE coupled with the HPLC method to environment monitoring analysis.

Dispersive solid-phase extraction based on zirconium metal-organic framework coupled with gas chromatography-mass spectrometry for determining sugar phosphates in biological samples.

BACKGROUND: Sugar phosphates (SPx) play important role in the metabolism of the organism. SPx such as glycerate 3-phosphate, fructose 6-phosphate and glucose 6-phosphate in biological samples have the poor stability, similar structure and low abundance, which make their separation and detection more challenging. METHOD: UiO-66-NH2 and ZrO2 coated SiO2(SBA-15) hard-core-shell adsorbents (UiO-66-NH2@SBA-15 and ZrO2@SBA-15) were synthesized, which were further used for dispersive solid-phase extraction for enriching the SPx in biological samples. The protocol was developed by UiO-66-NH2@SBA-15 and ZrO2@SBA-15 coupled with gas chromatography-mass spectrometry for the detection of trace SPx. The univariate experiment and response surface methodology were used to optimize the adsorption and desorption conditions. RESULTS: The adsorbents showed excellent adsorption capacity and specificity towards SPx, which were proved by adsorption and selective experiments. Under the optimized conditions, there were good linearity within the range of 5.0-5000.0 ng mL-1, low limits of detection (0.001-1.0 ng mL-1), low limits of quantification (0.005-5.0 ng mL-1) and good precision (relative standard deviation less than 14.7 % for intra-day and inter-day). The satisfactory recoveries (89.1-113.8 %) and precision (0.5-14.6 %) were obtained when the sorbents were used to extract SPx from serum, saliva and cell samples. Moreover, UiO-66-NH2@SBA-15 was applied to the quantitative analysis of SPx from gastric cancer patients, because of a higher adsorption capacity (169.5-196.1 mg g-1). CONCLUSIONS: UiO-66-NH2@SBA-15 showed great potential in the extraction of SPx in biological samples, which was beneficial to find out the metabolic change of SPx and explain the pathogenesis of the disease.

Deep eutectic solvent-functionalized amorphous UiO-66 for efficient extraction and ultrasensitive analysis of perfluoroalkyl substances in infant milk powder.

In this study, a convenient and effective method for determination of perfluoroalkyl substances (PFASs) in infant formula was developed based on a novel dispersive solid-phase extraction using deep eutectic solvent-functionalized amorphous UiO-66 (DES/aUiO-66) as sorbent. The synthesis of materials could be achieved without the use of complex and environmentally unfriendly procedures. Parameters were systematically investigated to establish a simple, fast, and efficient green pretreatment method. The method demonstrated high sensitivity, good precision, a detection limit of 0.330-0.529 ng·kg-1, and low matrix effects (< 12.8%). The mechanism for this material was elucidated by ab initio molecular dynamics (AIMD) simulations and quantum chemistry calculations. The presence of massive pore structures and collectively synergistic binding sites facilitated affinity adsorption toward PFASs. Finally, this method was applied to the monitoring of PFASs in 10 actual milk powder samples. This groundbreaking approach opens new possibilities for the advancement of analytical techniques and food safety monitoring.

Three-birds-with-one-stone: An eco-friendly and renewable humic acid-derived material application strategy for macrolide antibiotic detection and multifunctional composite film preparation.

This research proposes a simple and novel strategy for the green detection of antibiotics along with the reduction of microplastic and humic acid (HA) hazards. The entire process is based on a single-step solvent-sieving method to separate HA into insoluble (IHA) and soluble (SHA) components, subsequently recombining and designing the application according to the original characteristics of selected fractions in accordance with the zero-waste principle. IHA was applied as a dispersive solid phase extraction (DSPE) sorbent without chemical modification for the enrichment of trace MACs in complex biological matrices. The recovery of MACs was 74.06-100.84 % in the range of 2.5-1000 µg∙kg-1. Furthermore, SHA could be combined with biodegradable polyvinyl alcohol (PVA) to prepare multifunctional composite films. SHA endows the PVA film with favorable mechanical properties, excellent UV shielding as well as oxidation resistance performance. Compared with pure PVA, the tensile strength, toughness, antioxidant and UV-protection properties were increased to 157.3 Mpa, 258.6 MJ·m-3, 78.6 % and 60 % respectively. This study achieved a green and economically valuable utilization of all components of waste HA, introduced a novel approach for monitoring and controlling harmful substances and reducing white pollution. This has significant implications for promoting sustainable development and recovering valuable resources.

Preparation of deep eutectic solvent modified magnetic graphene oxide/metal organic framework nanocomposites for the extraction of three estrogens in cosmetics.

A novel magnetic dispersive solid phase extraction (MDSPE) procedure based on the deep eutectic solvent (DES) modified magnetic graphene oxide/metal organic frameworks nanocomposites (MGO@ZIF-8@DES) was established and used for the efficient enrichment of estradiol, estrone, and diethylstilbestrol in cosmetics (toner, lotion, and cream) for the first time. Then, the three estrogens were separated and determined by UHPLC-UV analysis method. In order to study the features and morphology of the synthesized adsorbents, various techniques such as FT-IR, SEM, and VSM measurements were executed. The MGO@ZIF-8@DES nanocomposites combine the advantages of high adsorption capacity, adequate stability in aqueous solution, and convenient separation from the sample solution. To achieve high extraction recoveries, the Box-Behnken design and single factor experiment were applied in the experimental design. Under the optimum conditions, the method detection limits for three estrogens were 20-30 ng g-1. This approach showed a good correlation coefficient (r more than 0.9998) and reasonable linearity in the range 70-10000 ng g-1. The relative standard deviations for intra-day and inter-day were beneath 7.5% and 8.9%, respectively. The developed MDSPE-UHPLC-UV method was successfully used to determine  three estrogens in cosmetics, and acceptable recoveries in the intervals of 83.5-95.9% were obtained. Finally, three estrogens were not detected in some cosmetic samples. In addition, the Complex GAPI tool was used to evaluate the greenness of the developed pretreatment method. The developed MDSPE-UHPLC-UV method is sensitive, accurate, rapid, and eco-friendly, which provides a promising strategy for determining hormones in different complex samples.

Highly Defective Zirconium-Based Metal-Organic Frameworks for the Efficient Adsorption and Detection of Sugar Phosphates in the Biological Sample.

Enrichment and quantification of sugar phosphates (SPx) in biological samples were of great significance in biological medicine. In this work, a series of zirconium-based metal-organic frameworks (MOFs) with different degrees of defects, namely, HP-UiO-66-NH2-X, were synthesized using acetic acid as a modulator and were utilized as high-capacity adsorbents for the adsorption of SPx in biological samples. The results indicated that the addition of acetic acid altered the morphology of HP-UiO-66-NH2-X, with corresponding changes in pore size (3.99-9.28 nm) and specific surface area (894.44-1142.50 m2·g-1). HP-UiO-66-NH2-10 showed the outstanding performance by achieving complete adsorption of all four SPx using only 80 µg of the adsorbent. The excellent adsorption efficiency of HP-UiO-66-NH2-10 was also obtained with a wide pH range and short adsorption time (10 min). Adsorption experiments demonstrated that the adsorption process involved chemical adsorption and multilayer adsorption. By utilizing X-ray photoelectron spectroscopy and density functional theory to explain the adsorption mechanism, it was found that various interactions (including coordination, hydrogen bonding, and electrostatic interactions) collectively contributed to the exceptional adsorption capability of HP-UiO-66-NH2-10. Those results indicated that the defect strategy not only increased the specific surface area and pore size, providing additional adsorption sites, but also reduced the adsorption energy between HP-UiO-66-NH2-10 and SPx. Moreover, HP-UiO-66-NH2-10 showed a low limit of detection (0.001-0.01 ng·mL-1), high precision (<13.77%), and accuracy (80.10-111.83%) in serum, liver, and cells, good stability, high selectivity (SPx/glucose, 1:100 molar ratio), and high adsorption capacity (292 mg·g-1 for SPx). The practical detection of SPx from human serum was also verified, prefiguring the great potentials of defective zirconium-based MOFs for the enrichment and detection of SPx in the biological medicine.

Dispersive Solid Phase Extraction of Melatonin with Graphene/Clay Mixtures and Fluorescence Analysis in Surfactant Aqueous Solutions.

In this work, the dispersive solid phase extraction (dSPE) of melatonin using graphene (G) mixtures with sepiolite (SEP) and bentonite (BEN) clays as sorbents combined with fluorescence detection has been investigated. The retention was found to be quantitative for both G/SEP and G/BEN 4/96 and 10/90 w/w mixtures. G/clay 4/96 w/w mixtures were selected to study the desorption process since the retention was weaker, thus leading to easier desorption. MeOH and aqueous solutions of the nonionic surfactant Brij L23 were tested as desorbents. For both clays and an initial sample volume of 25 mL, a percentage of melatonin recovery close to 100% was obtained using 10 or 25 mL of MeOH as desorbent. Further, using a G/SEP mixture, 25 mL as the initial sample volume and 5 mL of MeOH or 60 mM Brij L23 solution as the desorbent, recoveries of 98.3% and 90% were attained, respectively. The whole method was applied to herbal tea samples containing melatonin, and the percentage of agreement with the labeled value was 86.5%. It was also applied to herbal samples without melatonin by spiking them with two concentrations of this compound, leading to recoveries of 100 and 102%.

Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples.

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4'-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214-327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

Carboxyl-functionalized covalent organic frameworks for the extraction of malachite green and crystal violet in environmental water samples prior to quantification by high-performance liquid chromatography.

In this study, monodisperse, uniform, and spherical covalent organic frameworks (COFs) were synthesized using 1,3,5-tris (4-aminophenyl) benzene and 1,3,5-tricarboxaldehyde benzene at room temperature. Post-modification of 6-aminocaproic acid on the COFs yielded carboxyl-modified COFs (COFs-COOH). The modification enhanced the hydrophilicity and adsorption efficiencies of COFs-COOH for malachite green (MG) and crystal violet (CV). A COFs-COOH-based dispersive solid-phase extraction coupled with high-performance liquid chromatography was developed for the analysis of MG and CV. The method showed a linear range from 10 to 1000 ng/mL with detection limits of 1.82 and 0.70 ng/mL for MG and CV detection, respectively. The recoveries of MG and CV from water samples collected from fish farms and markets ranged from 91.63% to 107.10% with relative standard deviations below 5%. Reproducibility tests demonstrated that the adsorption efficiencies of COFs-COOH were maintained at above 85.86% over 15 cycles. The study verified the potential of COFs-COOH as sorbents for the enrichment and separation of triphenylmethane dyes from complex samples.

Dihydroxyl modified UiO-66 as dispersive solid-phase extraction sorbent coupled with ultra-high performance liquid chromatography tandem mass spectrometry for detection of neonicotinoid insecticides.

The extensive usage of neonicotinoid insecticides (NIs) has raised many concerns about their potential harm to environment and human health. Thus, it is of great importance to develop an efficient and reliable method to determine NIs in food samples. In this work, three Zr4+-based metal-organic frameworks functionalized with various numbers of hydroxyl groups were fabricated with a facile one-pot solvothermal method. Among them, dihydroxy modified UiO-66 (UiO-66-(OH)2) exhibited best adsorption performance towards five target NIs. Then, a sensitive and efficient method for detection of NIs from vegetable and fruit samples was established based on dispersive solid phase extraction (dSPE) with UiO-66-(OH)2 as adsorbent coupled with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Key parameters affecting the dSPE procedure including amounts of adsorbent, adsorption time, eluent solvents and desorption time were investigated. Under the optimal conditions, rapid adsorption of NIs within five minutes was achieved due to the high affinity of UiO-66-(OH)2 towards NIs. The developed method exhibited high sensitivity with limits of detection (LODs) varied from 0.003 to 0.03 ng/mL and wide linearity range over 3-4 orders of magnitude from 0.01 to 500 ng/mL. Furthermore, the established method was applied for determining trace NIs from complex matrices with recoveries ranging from 74.6 to 99.6 % and 77.0-106.8 % for pear and tomato samples, respectively. The results indicate the potential of UiO-66-(OH)2 for efficient enrichment of trace NIs from complex matrices.

Ultrasonic-induced grafted lanthanum sulfide decorated multi-walled carbon nanotube onto bacterial cellulose applied for adsorption of pesticides in environmental waters.

A new biosorbent was fabricated by modification of bacterial cellulose biopolymer grafted with lanthanum sulfide decorated carboxylated multiwall carbon nanotube (La2S3@MWCNT@BC). The sorbent was employed in a green alternative dispersive-solid phase extraction of a variety of 14 pesticides in environmental water samples. The analyses were performed using GC-µECD. The properties and structure of La2S3@MWCNT@BC nanocomposite were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and adsorption-desorption isotherms. The composition of the sorbent was also investigated to evaluate the adsorptive properties of its constituents. The impact of various parameters influencing extraction efficacies such as sorbent dose, adsorption time, sample pH, ionic strength, and desorption conditions was investigated. The method was validated by specificity, matrix effect % (-0.4 to -7.4), enrichment factor (4-10), limits of quantification (0.007-0.31 µg L-1), matrix-matched calibration linearity (0.01-200 µg L-1), determination coefficients (r2=0.9921-0.9998), and precision. The optimized method was applied for the analysis of multiclass pesticides in seven environmental and drinking waters and the recoveries were obtained in the 81-108 % range with RSDs of 2.5-4.7 %. This paper is the first report on the synthesis and use of La2S3@MWCNT@BC nanocomposite to extract pesticides from different water samples. The greenness of the procedure was evaluated by the AGREE protocols.

Development of dispersive solid phase extraction based on magnetic metal organic framework for the extraction of sunitinib in biological samples and its determination by high performance liquid chromatography-tandem mass spectrometry.

Herein, a simple, sensitive, and reliable dispersive solid phase extraction was reported for the efficient extraction of sunitinib from biological samples. To facilitate the extraction of the desired analyte from urine and plasma samples, magnetic MIL-101Cr (NH2) @SiO2 @ NiFe2O4 was synthesized by a hydrothermal method and applied as an effective sorbent during the extraction process. After adsorption of the drug using 10 mg of MIL-101Cr (NH2) @ SiO2 @ NiFe2O4 nanoparticles through vortexing (1 min), the sorbent was separatedfrom the sample solution using a magnet. To eluate the drug, the sorbent containing the sunitinib was contacted with 100 µL dimethylformamide. The eluent was analyzed by high performance liquid chromatography-tandem mass spectrometry. Reasonable validation data consisting of low limits of detection (0.14, 0.35, and 0.70 ng mL-1 in deionized water, plasma, and urine) and quantification (0.48, 1.2, and 2.4 ng mL-1 in deionized water, plasma, and urine, respectively), a wide linear range of the calibration curve (0.48-200, 1.2-200, and 2.4-100 ng mL-1 in deionized water, plasma, and urine, respectively) good extraction recovery (76 %), and low relative standard deviations for inter- and intra-day precisions (6.9 %) were obtained by the method. Eventually, the proposed procedure was effectively implemented on both plasma and urine samples, yielding successful outcomes.

Application of cobalt-cerium-iron ternary layered double hydroxide for extraction of perfluorooctane sulfonate followed by HPLC-MS/MS analysis.

Herein, Ce-doped CoFe layered double hydroxide (LDH), noted as CoCeFe ternary LDH, was prepared using the co-precipitation route. Prosperous synthesis of CoFe LDH and successful partial replacement of iron cations with cerium cations in CoCeFe ternary LDH were confirmed by X-ray diffraction patterns, energy-dispersive X-ray spectroscopy, and elemental dot-mapping images. Nanosheet morphology was recognized for both CoFe LDH and CoCeFe ternary LDH from scanning electron microscopy and transmission electron microscopy micrographs. In the following, a dispersive solid phase extraction (DSPE) method was developed using the synthesized CoCeFe ternary LDH as a sorbent for extracting perfluorooctanesulfonic acid (PFOS) from wastewater samples. For the selective analysis of PFOS, high-performance liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS) in multiple reaction monitoring mode was used. Analytical parameters such as the limit of detection equal to 0.02 µg/L, with a linear range of 0.05-300 µg/L, the limit of quantification equal to 0.05 µg/L, and an enrichment factor equal to 23.3 were achieved for PFOS at the optimized condition (sorbent: 5 mg of CoCeFe ternary LDH, eluent type and volume: 150 µL mobile phase, pH: 3, adsorption time: 3 min, and desorption time: 5 min). The developed strategy for the analysis of PFOS was tested in real wastewater samples, including copper mine and petrochemical wastewater. The amount of analytes in real samples was calculated using the standard addition method, and good relative recovery in the range of 86%-105% was obtained. The main novelty of this research is the application of CoCeFe ternary LDH to extract the PFOS from wastewater using the DSPE method for determination by HPLC-MS/MS.

Porous poly(bismaleimide-co-divinylbenzene) microspheres as dispersive solid-phase extraction adsorbent coupled to high-performance liquid chromatography for the determination of triazine herbicide residues in vegetable samples.

In this work, monodisperse and nano-porous poly(bismaleimide-co-divinylbenzene) microspheres with large specific surface area (427.6 m2 /g) and rich pore structure were prepared by one-pot self-stable precipitation polymerization of 2,2'-bis[4-(4-maleimidophenoxy) phenyl] propane and divinylbenzene. The prepared poly(bismaleimide-co-divinylbenzene) microspheres were employed as dispersive solid-phase extraction (DSPE) adsorbent for the extraction of triazine herbicides. Under optimized conditions, good linearities were obtained between the peak area and the concentration of triazine herbicides in the range of 1-400 µg/L (R2 ≥ 0.9987) with the limits of detection of 0.12-0.31 µg/L. Triazine herbicides were detected using the described approach in vegetable samples (i.e., cucumber, tomato, and maize) with recoveries of 93.6%-117.3% and relative standard deviations of 0.4%-3.5%. In addition, the recoveries of triazine herbicides remained above 80.7% after being used for nine DSPE cycles, showing excellent reusability of poly(bismaleimide-co-divinylbenzene) microspheres. The adsorption of poly(bismaleimide-co-divinylbenzene) microspheres toward triazine herbicides was a monolayer and chemical adsorption. The adsorption mechanism between triazine herbicides and adsorbents might be a combination of hydrogen bonding, electrostatic interaction, and π-π conjugation. The results confirmed the potential use of the poly(bismaleimide-co-divinylbenzene) microspheres-based DSPE coupled to the high-performance liquid chromatography method for the detection of triazine herbicide residues in vegetable samples.

[Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials].

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 µm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 µg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 µg/L and 0.03-0.42 µg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 µg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.

Regulating the defects of MIL-101(Cr) for the efficient and simultaneous determination of eleven plant growth regulators in fresh fruit juice.

This work presents an efficient sorbent for plant growth regulators (PGRs) by regulating the defects of a metal-organic framework MIL-101(Cr). Using the regulated MIL-101(Cr), we developed a simple and effective method for the simultaneous determination of eleven PGRs in fresh fruit juice. The extraction conditions were optimized by an orthogonal array design. Under optimal conditions, the method showed a satisfactory limit of detection (0.1-1.2 ng/g), recovery rates (83.4-110.2 %), and precision (2.9-18.0 % for intra-day and 2.7-10.8 % for inter-day), as well as a greatly suppressed matrix effect. Notably, regulating the defects significantly enhanced the desorption of PGRs on MIL-101(Cr). The sorbent didn't need to be destroyed to release the adsorbed PGRs and could be reused at least 6 times. Furthermore, the defects of MIL-101(Cr) and interactions between the sorbent and PGRs were studied by TGA, ATR-IR, XPS, NH3-TPD and UV-Vis DRS.

A new methodology to reveal potential nucleic acid modifications associated with the risk of endometrial cancer through dispersive solid-phase extraction coupled with UHPLC-QE-Orbitrap-MS/MS and HPLC-UV.

Nucleic acid modifications have attracted increasing attention in recent years since they have been found to be related to a number of diseases including cancer. Previous studies have shown that the early development of endometrial cancer (EC) is often accompanied by changes in methylation levels of related genes, and the expression of related proteins that regulate reactive oxygen species (ROS) shows significant differences in EC cells and tissues. However, it has not been reported whether nucleic acid modifications related to methylation or ROS can serve as biomarkers for EC. Accurate quantification of these nucleic acid modifications still has challenges because their amounts in urine are very low and the interferences in urine are complicated. In this study, a novel dispersive solid-phase extraction (DSPE) method based on chitosan-carbon nanotube-Al2O3 (CS-CNT-Al2O3) has been established for the analysis of 5-hydroxymethyluracil (5 mU), 5-methyl-2'-deoxycytidine (5-mdC), 5-hydroxymethyl-2'-deoxycytidine (5-hmdC), 5-formyl-2'-deoxycytidine (5-fdC), and 8-hydroxy-2'-deoxyguanosine (8-OHdG) in EC patient urine samples coupled with UHPLC-QE-Orbitrap-MS/MS and HPLC-UV. Firstly, the synthesis of the CS-CNT-Al2O3 nanocomposite was conducted by a sono-coprecipitation method and was characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), and Fourier transform infrared (FTIR). Under the optimal extraction conditions of DSPE, we successfully quantified 5 mU, 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG in urine samples from 37 EC patients and 39 healthy controls. The results showed that there were significant differences in the levels of 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG in EC patients compared to the healthy control group. The receiver operator characteristic (ROC) curve analysis was carried out to evaluate the potential of 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG to distinguish EC patients from healthy volunteers. The area under the curve (AUC) for 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG was 0.7412, 0.667, 0.8438, and 0.7981, respectively. It indicated that 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG had certain potential in distinguishing between EC patients and healthy volunteers and they could act as potential non-invasive biomarkers for early diagnosis of EC. Moreover, the present study would stimulate investigations of the effects of nucleic acid modifications on the initiation and progression of EC.

Facile Preparation of Magnetic COF-on-COF for Rapid Adsorption and Determination of Sulforaphane from Cruciferous Vegetables.

Sulforaphane (SFN) is a natural isothiocyanate compound widely abundant in cruciferous vegetables with multiple bioactive functions. However, traditional analytical methods for the extraction and determination of SFN are cumbersome, time-consuming, and low sensitivity with large amounts of organic solvents. Herein, novel magnetic COF-on-COFs (MB-COFs) were fabricated using Fe3O4 as a magnetic core and COFs-1 grown with COFs-2 as a shell, and they were used as efficient adsorbents of magnetic dispersive solid-phase extraction for rapid quantification of SFN in cruciferous vegetables by combining with HPLC-MS/MS. At the optimal ratio of COFs-1 to COFs-2, MB-COFs had a spherical cluster-like structure and a rough surface, with a sufficient magnetic response for rapid magnetic separation (1 min). Due to the introduction of Fe3O4 and COFs-2, MB-COFs exhibited outstanding extraction efficiencies for SFN (92.5-97.3%), which was about 18-72% higher than that of the bare COFs. Moreover, MB-COFs showed good adsorption capacity (Qm of 18.0 mg/g), rapid adsorption (5 min) and desorption (30 s) to SFN, and favorable reusability (≥7 cycles) by virtue of their unique hierarchical porous structure. The adsorption kinetic data were well fitted by the pseudo-second-order, Ritchie-second-order, intra-particle diffusion, and Elovich models, while the adsorption isotherm data were highly consistent with the Langmuir, Temkin, and Redlich-Peterson models. Finally, under the optimized conditions, the developed method showed a wide linear range (0.001-0.5 mg/L), high sensitivity (limits of quantification of 0.18-0.31 µg/L), satisfactory recoveries (82.2-96.2%) and precisions (1.8-7.9%), and a negligible matrix effect (0.82-0.97). Compared to previous methods, the proposed method is faster and more sensitive and significantly reduces the use of organic solvents, which can achieve the efficient detection of large-scale samples in practical scenarios. This work reveals the high practical potential of MB-COFs as adsorbents for efficient extraction and sensitive analysis of SFN in cruciferous vegetables.

Investigation of low-temperature partitioning with dispersive solid-phase extraction for quantification of pesticides in apples followed by electrospray-ionization mobility spectrometry: Comparison with conventional procedure.

Ion mobility spectrometry (IMS) has a promising application prospect in food surveillance. However, due to the complexity of food matrix and trace levels of pesticide residues, the effective and rapid detection of pesticides by IMS has been a challenge, especially when using electrospray ionization (ESI) as an ion source. In this study, low-temperature partitioning with dispersive solid-phase extraction (LTP-dSPE) was explored and compared with conventional procedures. Both methods were validated for the quantification of eight pesticides in apples, obtaining a limit of detection (LOD) of 0.02-0.12 mg/kg for LTP-dSPE and 0.02-0.09 mg/kg for conventional solid-phase extraction (SPE), lower than those usually stipulated by government legislation in food matrices. For LTP-dSPE, the matrx effect (ME) ranged from -16.3 to -68.6 %, lower than that for the SPE method, ranging from -70.0 to -92.9 %. The results showed satisfactory efficiency and precision, with recovery values ranging from 67.9 to 115.4 % for LTP-dSPE and from 62.0 to 114.8 % for conventional SPE, with relative standard deviations below 13.0 %. Notably, the proposed LTP-dSPE/ESI-IMS has been shown to be more cost-effective, easier to use, more environment-friendly, more accessible, and, most importantly, less matrix effect than the conventional method, thereby being suitably applicable to a wide range of food safety applications.