Development, validation, and implementation of an ultratrace analysis method for the determination of moenomycin A, in aquatic animal products.

Moenomycin A, an antimicrobial growth promoter widely used as an additive in aquaculture feedstuffs, has been restricted for use in the European Union and China due to its potential risk of promoting resistant strains of pathogenic bacteria and causing residues in aquatic animal products. Although methods for analyzing moenomycin A in feedstuffs have been developed, no established method exists for aquatic matrices. In this study, we present, for the first time, a sensitive and validated high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for the determination of moenomycin A in aquatic animal products. Samples were extracted using methanol and purified with the QuEChERS method employing C18 sorbent. The aliquot was dried under a nitrogen stream, reconstituted with methanol-water solvent, and analyzed by HPLC-MS/MS. The developed method exhibited good linearity (r2 > 0.995) over a wide concentration range (1-100 µg/L) and a low limit of detection (1 µg/kg). Average recoveries ranged between 70 and 110% at spiked concentrations of 1, 50, and 100 µg/kg, with associated intra- and inter-day relative standard deviations of 1.25 to 7.32% (n = 6) and 2.91 to 10.08% (n = 3), for different representative aquatic animal production, respectively. To the best of our knowledge, this is the first reported HPLC-MS/MS method for the quantification of moenomycin A in aquatic animal products. The new approach was effectively employed in the analysis of moenomycin A across various aquatic samples.

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.

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.

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.

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.

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.

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%.

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.

Development of dispersive solid phase extraction method for the preconcentration of parathion ethyl as a simulant of nerve agent sarin from soil, plant and water samples prior to GC-MS determination.

In the presented study, an efficient and fast analytical method was developed for the determination of parathion ethyl as sarin simulant by gas chromatography-mass spectrometry (GC-MS). Dispersive solid phase extraction (DSPE) was performed to concentrate parathion ethyl from soil, plant and water samples. Reduced graphene oxide-iron (II, III) oxide (rGO-Fe3O4) nanocomposite was used as an adsorbent to collect the target analyte from the aqueous sample solutions. After the optimization of extraction/preconcentration parameters, optimum conditions for adsorbent amount, eluent type, mixing type/period, eluent volume and initial sample volume were determined as 15 mg, acetonitrile, vortex/30 s, 100 µL and 10 mL, respectively. Under the optimum conditions, analytical performance of the developed DSPE-GC-MS method was evaluated in terms of limit of detection (LOD), limit of quantitation (LOQ) and dynamic range. Dynamic range, LOD and LOQ values were figured out to be 0.94-235.15 µg/kg, 0.41 µg/kg and 1.36 µg/kg (mass based), respectively. Satisfactory percent recovery results (90.3-125% for soil, 93.5-108.7% for plant, 88.5-112.9% for tap water) were achieved for soil, plant and tap water samples which proved the accuracy and applicability of the developed method. It is predicted that the DSPE-GC-MS method can be accurately used for the detection of sarin in soil, plant and water samples taken from war territories.

A novel removal of Ni2+ ions from water solutions using dispersive solid-phase extraction method with nano Fe3O4/chitosan-acrylamide hydrogel.

The effluent release containing heavy metals as Ni2+ ions has drastic risks to both the natural environment and human health. In this research, the nano Fe3O4/chitosan-acrylamide hydrogel was prepared as a novel nano sorbent for dispersive solid-phase extraction of Ni2+ ions and applied to the water sample solution. The pH, amount and type of elution solvent, the extraction time, etc. were optimized to improve the efficiency of the proposed method. Analytical parameters such as concentration factor and relative standard deviation (%) were achieved as 33.3 and 1.8%, respectively. The capacity in equilibrium sorption was calculated at 22.54 mg g-1. Furthermore, to estimate the adsorption mode, Freundlich, Langmuir, and Temkin models were fitted with experimental isotherm data. Besides, to check the basic process of the metal adsorption mechanism, pseudo-first-order, pseudo-second-order, and Roginsky-Zeldovich models were investigated and the results were fitted with the pseudo-second-order model. The value of change in entropy (⊿S) obtained is -65.24 (J(mol K)-1). Negative values of change in enthalpy, ⊿H in (kJ mol-1) is -24.45 (kJ mol-1) which indicates both physical and chemical adsorptions involved in the process of adsorption. Finally, the nano Fe3O4/chitosan-acrylamide hydrogel exhibited high performance to remove the Ni2+ ions from water sample solution.

Determination of nitroimidazole antibiotics based on dispersive solid-phase extraction combined with capillary electrophoresis.

For a long time, the detection of nitroimidazole antibiotics (NIABs) has been a research focus in environmental analytical chemistry. In this work, a novel technique for the analysis of nitroimidazoles was established based on capillary electrophoresis (CE). UiO-66, synthesized using a solvothermal method, was utilized as an adsorbent in the dispersive solid-phase extraction (DSPE) of five different NIABs. The separation and detection of NIABs in environmental water samples were accomplished using the CE diode array detection method. The optimal extraction conditions were obtained after systematically studying the effects of adsorption time, the amount of extractant, and elution solvent on extraction efficiency. According to the results of the study, the limit of detections of the five NIABs were between 16 and 97 ng/mL, the relative standard deviations were between 0.32% and 0.55%, and the spike recoveries were between 87.43% and 104.8%. This study presents a novel technique for measuring NIABs in complex water samples.

UiO-66-NH2: a recyclable and efficient sorbent for dispersive solid-phase extraction of fluorinated aromatic carboxylic acids from aqueous matrices.

The present study describes the trace analysis of 23 fluorinated aromatic carboxylic acids based on the dispersive solid-phase extraction (dSPE) technique using UiO-66-NH2 MOF as efficient, recyclable sorbent, and GC-MS negative ionization mass spectrometry (NICI MS) as determination technique. All 23 fluorobenzoic acids (FBAs) were enriched, separated, and eluted in a shorter retention time; the derivatization was done by pentafluorobenzyl bromide (1% in acetone), in which the use of inorganic base K2CO3 was improved by triethylamine to increase the lifespan of the GC column. The performance of UiO-66-NH2 was evaluated by dSPE in Milli-Q water, artificial seawater, and tap water samples, and the impact of various parameters on the extraction efficiency was investigated by GC-NICI MS. The method was found to be precise, reproducible, and applicable to the seawater samples. In the linearity range, the regression value was found to be >0.98; LOD and LOQ were found to be in the range of 0.33-1.17 ng/mL and 1.23-3.33 ng/mL, respectively; and the value of the extraction efficiency was found to range between 98.45 and 104.39% for Milli-Q water samples, 69.13-105.48% for salt-rich seawater samples, and 92.56-103.50% for tap water samples with a maximum RSD value of 6.87% that confirms the applicability of the method to different water matrices.

Dispersive solid phase extraction of metronidazole and clarithromycin from human plasma using a ß-cyclodextrin grafted polyethylene polymer composite.

In this work, for the first time, a polymeric composite based on ß-cyclodextrin grafted with polyethylene has been prepared through ball milling and used as an efficient sorbent for dispersive solid phase extraction of metronidazole and clarithromycin from plasma samples. The prepared sorbent was characterized using Fourier transform infrared spectrophotometry, X-ray diffraction, and scanning electron microscopy. In the extraction process, after precipitating the proteins, the sorbent was added into the sample solution, and the mixture was vortexed to facilitate and speed up the sorption of the analytes onto the sorbent surface. After centrifuging, the sorbent particles were contacted with methanol to elute the analytes under the vortexing process. After this step, an aliquot of the eluate was taken and injected into high-performance liquid chromatography-diode array detector for quantitative analysis. Under the optimum extraction conditions, the extraction recoveries for metronidazole and clarithromycin were 76 and 83%, respectively. The limits of detection were 2.6 and 2.2 ng/ml for metronidazole and clarithromycin, respectively. The repeatability of the offered approach, expressed as relative standard deviation, was equal to or less than 4.7%. Finally, the method was successfully applied to plasma samples of the patients treated with metronidazole and clarithromycin.

Polycarbonate-coated magnetic nanoparticles for the extraction of imipramine and its primary metabolite from urine.

This study introduces a reliable and inexpensive magnetic dispersive solid phase extraction to extract imipramine and its primary metabolite (desipramine) from urine samples. To accomplish this aim, Fe3 O4 magnetic nanoparticles were synthesized by sonication, subsequently, polycarbonate was precipitated gradually onto the surface of them to form the adsorbent. Extraction recoveries of 85% and 76%, enrichment factors of 57 and 51, limits of detection of 2.5 and 2.8 µg/L, and limits of quantification of 8.3 and 9.3 µg/L were obtained for imipramine and desipramine under the optimal conditions, respectively. In addition, relative standard deviations for intra- (n = 6) and inter-day (n = 5) precisions at two concentrations (50 and 100 µg/L of each analyte) were less than or equal to 4%. Short extraction time, good repeatability, high enrichment factors, and simplicity are the main advantages of the proposed method.

Facile synthesis of spherical covalent organic frameworks for enrichment and quantification of aryl organophosphate esters in mouse serum and tissues.

Here, an imine-linked-based spherical covalent organic framework (COF) was prepared at room temperature. The as-synthesized spherical COF served as an adsorbent in dispersive solid-phase extraction (dSPE), by its virtue of great surface area (1542.68 m2 /g), regular distribution of pore size (2.95 nm), and excellent stability. Therefore, a simple and high-efficiency dispersive solid phase extraction method based on a spherical COF coupled with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established to determine aryl organophosphate esters in biological samples. This approach displayed favorable linearity in the range of 10.0-1000.0 ng/L (r > 0.9989), a high signal enhancement factor (58.8-181.8 folds) with low limits of detection (0.3-3.3 ng/L). Moreover, it could effectively eliminate complex matrix interference to accurately extract seven aryl organophosphate esters from mouse serum and tissue samples with spiked recoveries of 82.0%-117.4%. The as-synthesized spherical COF has been successfully applied in sample preparation. The dSPE-HPLC-MS/MS method based on a spherical COF has potential application to study the pollutants' metabolism in vivo.

Dispersive solid-phase extraction of alkaloids and polyphenols using borate hypercrosslinked polymers.

In this study, a borate hyper-crosslinked polymer was synthesized by crosslinking 1-naphthalene boric acid and dimethoxymethane via the Friedel-Crafts reaction. The prepared polymer exhibits excellent adsorption performance toward alkaloids and polyphenols with maximum adsorption capacities ranging from 25.07 to 39.60 mg/g. Adsorption kinetics and isotherms model results indicated the adsorption was a monolayer and chemical process. Under the optimal extraction conditions, a sensitive method was established for the simultaneous quantification of alkaloids and polyphenols in green tea and Coptis chinensis by coupling with the proposed sorbent and ultra-high performance liquid chromatography detection. The proposed method exhibited a wide linear range of 5.0-5000.0 ng/ml with R2 ≥ 0.99, a low limit of detection (0.66-11.25 ng/ml), and satisfactory recoveries (81.2%-117.4%). This work provides a simple and convenient candidate for the sensitive determination of alkaloids and polyphenols in green tea and complex herbal products.

Application of in-situ formed polymer-based dispersive solid phase extraction in combination with solidification of floating organic droplet-based dispersive liquid-liquid microextraction for the extraction of neonicotinoid pesticides from milk samples.

An in-situ formed polymer-based dispersive solid phase extraction in combination with solidification of floating organic droplet-based dispersive liquid-liquid microextraction was developed for the extraction of neonicotinoid pesticides from milk samples. The extracted analytes were determined using high-performance liquid chromatography-diode array detector. In this approach, after precipitating the proteins of milk using a zinc sulfate solution, the supernatant phase (containing sodium chloride) was transferred into another glass test tube, and a homogenous solution of polyvinylpyrrolidone and a suitable water-miscible organic solvent was rapidly injected into it. By this step, the polymer particles were re-produced and the analytes were extracted onto the sorbent surface. In the following step, the analytes were eluted with an appropriate organic solvent to use in the following solidification of floating organic droplet-based dispersive liquid-liquid microextraction step that was done to acquire the low limits of detection. Under the optimized conditions, satisfactory results consisting of low limits of detection (0.13-0.21 ng/ml) and quantification (0.43-0.70 ng/ml), high extraction recoveries (73%-85%), and enrichment factors (365-425), and good repeatability (relative standard deviations equal or less than 5.1% and 5.9% for intra- and inter-day precisions, respectively) were obtained.

Dispersive solid phase extraction based on cross-linked hydroxypropyl ß-cyclodextrin polymers for simultaneous enantiomeric determination of three chiral triazole fungicides in water.

An efficient method is presented for simultaneous enantioselective determination of three chiral triazole fungicides (namely paclobutrazol, hexaconazole, and diniconazole) in water samples by DSPE-HPLC-UV. The perfect chiral separation of the enantiomers was achieved on a Chiralpak IH column within 15 min. In order to adsorb and enrich the analytes from water matrices, a cross-linked hydroxypropyl ß-cyclodextrin polymer was synthesized. The prepared material exhibited good adsorption capacity, which was assessed by adsorption kinetic and adsorption thermodynamic experiments. One-variable-at-a-time and the response surface methodology were used to optimize the extraction parameters. Under the optimum sample preparation conditions, good linearity (2.0 ~ 800 µg L-1, R2 ≥ 0.9978), detection limits (0.6 to 1.0 µg L-1), quantitation limits (2.0 to 3.2 µg L-1), recoveries (86.7 ~ 105.8%), and the relative standard deviation (intra-day RSD ≤ 3.7%, inter-day RSD ≤ 5.1%) were obtained, satisfying the requirements of pesticides residues determination. These results demonstrated that the proposed method was applicable for routine determination of chiral triazole fungicide residues in water samples.

Slice-layer COFs-aerogel: a regenerative dispersive solid-phase extraction adsorbent for determination of ultra-trace quinolone antibiotics.

A novel type of three-dimensional network structure, covalent organic frameworks (COFs) aerogel, was fabricated and applied to dispersive solid-phase extraction (dSPE) of quinolone antibiotics (QAs). Density functional theory (DFT) was applied to investigate the possible interaction mechanism and results confirmed that the strong adsorption affinity is attributed to the intralayer hydrogen bonds and π-π interaction. Furthermore, a sensitive analytical method based on COFs-aerogel for determining quinolone antibiotics residues in water and honey samples was developed and HPLC-MS/MS was used for sample detection and quantification. Under the optimal conditions, COFs-aerogel exhibited a wide linearity (0.1-500 ng∙L-1), low limits of detection (0.02-0.06 ng∙L-1), and good precision (RSD ˂ 10%) for selected QAs. A preliminary practical application of the developed method was proved by the efficient detection of quinolone antibiotics in water and food samples with good recoveries (68.2-104% and 64.0-100% for water and honey samples, respectively). Combining the experimental data with theoretical calculation, results illustrated that COFs-aerogel holds a great potential to capture contaminants and address environmental and food safety issues.

Facile synthesis of hollow microtubular COF as enrichment probe for quantitative detection of ultratrace quinones in mice plasma with APGC-MS/MS.

A hollow microtubular covalent organic framework (denoted as TatDha-COF) was synthesized by solvothermal method for the enrichment and determination of quinones. The TatDha-COF showed large specific surface area (2057 m2 g-1), good crystal structure, ordered pore size distribution (2.3 nm), stable chemical properties and good reusability. Accordingly, a simple and efficient method based on dispersive solid-phase extraction (d-SPE) and atmospheric pressure gas chromatography tandem mass spectrometry (APGC-MS/MS) was developed for the determination of quinones in complex samples. The established method demonstrated a wide liner range, good linearity (r>0.9990), high enrichment factors (EFs, 24-69-folds) and low detection limits (LODs, 0.200-30.0 pg L-1, S/N≥3). On this basis, the suggested method was successfully applied to sensitively detect the eight ultratrace quinones in mice plasma. Overall, the established method has provided a powerful tool for the enrichment and detection of ultratrace quinones in complex samples, presenting the promising application of TatDha-COF in sample pretreatment.