Preparation of highly hydrophilic magnetic nanoparticles with anion‐exchange ability and their application for the extraction of non‐steroidal anti‐inflammatory drugs in environmental samples

Diallyldimethylammonium chloride modified magnetic nanoparticles were synthesized by the “thiol‐ene” click chemistry reaction. Diallyldimethylammonium chloride rendered the material plenty of quaternary ammonium groups, and thus the excellent aqueous dispersibility and anion‐exchange capability. The novel material was then used as the magnetic solid‐phase extraction sorbent to extract eight non‐steroidal anti‐inflammatory drugs from water samples. Combined with high‐performance liquid chromatography and ultraviolet detection, under the optimal conditions, the developed method exhibited wide linearity ranges (1–1000, 2–1000, and 5–1000 ng/mL) with recoveries of 88.0–108.6% and low limits of detection (0.3–1.5 ng/mL). Acceptable precision was obtained with satisfactory intra‐ and inter‐day relative standard deviations of 0.4–4.4% (n = 3) and 1.1–5.5% (n = 3), respectively. Batch‐to‐batch reproducibility was acceptable with relative standard deviations <9.7%. The hydrophilic magnetic nanoparticle featured with quaternary ammonium groups showed high analytical potential for acidic analytes in environmental water samples.     

Cotton thread modified with ionic liquid copolymerized polymer for online in‐tube solid‐phase microextraction and HPLC analysis of nonsteroidal anti‐inflammatory drugs

Cotton fiber is a biodegradable material that possesses properties such as high specific area, adjustable shape, and hygroscopicity. In this work, organic polymer was directly in situ grown on the surface of cotton thread and packed into a poly(ether ether ketone) tube for online in‐tube solid‐phase microextraction. The novel strategy solves the problems like high backpressure and tedious optimization process of normal monolithic polymer‐based in‐tube solid‐phase microextraction capillary. The quaternary ammonium typed ionic liquid of 1‐allyl‐methylimidazolium chloride, 4‐vinylbiphenyl, and ethylene dimethacrylate were co‐polymerized and in situ grown on the surface of cotton thread as extraction phase. The solid‐phase microextraction tube showed excellent performance for the extraction of three nonsteroidal anti‐inflammatory drugs including ketoprofen, naproxen, and flurbiprofen due to the strong ion exchange and hydrophobic interactions. After online coupling with a high‐performance liquid chromatography system by six‐port valve, the method was applied for the quantitative analysis of nonsteroidal anti‐inflammatory drugs in human plasma samples showing good enrichment performance (enrichment factor between 263 and 279), high sensitivity, good linearity, and good reproducibility.     

Facile synthesis of magnetic zinc metal‐organic framework for extraction of nitrogen‐containing heterocyclic fungicides from lettuce vegetable samples

We present a simple method for the fabrication of a magnetic amino‐functionalized zinc metal‐organic framework based on a magnetic graphene oxide composite. The resultant framework exhibited a porous 3D structure, high surface area and good adsorption properties for nitrogen‐containing heterocyclic fungicides. The adsorption process and capacity indicated that the primary adsorption mechanism might be hydrogen bonding and π‐π conjugation. In addition, an optimized protocol for magnetic solid phase extraction was developed (such as adsorbent content, pH, and desorption solvent), and utilized for the extraction of nitrogen‐containing heterocyclic fungicides from vegetable samples. Quantitation by high performance liquid chromatography coupled with tandem mass spectrometry offered a detection limit of 0.21–1.0 μg/L (S/N = 3) with correlation coefficients larger than 0.9975. These results demonstrate that magnetic amino‐functionalized zinc metal‐organic framewor is a promising adsorbent for the extraction and quantitation of nitrogen‐containing heterocyclic fungicides.     

Preparation of dummy template‐imprinted polymers for the rapid extraction of nonsteroidal anti‐inflammatory drugs residues in aquatic environmental samples

A molecularly imprinted polymer was synthesized and applied as a sorbent in the solid‐phase extraction device. The imprinted polymer was characterized by fourier‐transform infrared spectroscopy and scanning electron microscope. The results revealed that imprinted polymer possess sensitive selectivity and reliable adsorption properties for five NSAIDs. The imprinted polymer was successfully applied to the pre‐concentration for five NSAIDs in different water samples prior to UPLC‐MS/MS. In the early studies, several factors were investigated, including pH adjustment, the kind of elution solvent and the volume of elution solvent. Finally, we found that the pH 5 and an aliquot of 2 mL methanol were suitable for the water samples. The limits of detection and limits of quantitation of five nonsteroidal anti‐inflammatory drugs varied from 0.007 to 0.480 μg L⁻¹ and 0.03 to 1.58 μg L⁻¹, respectively. The spiking recoveries of the target analytes were 50.33‐127.64% at the levels of 0.2 μg L⁻¹, 2 μg L⁻¹ and 5 μg L⁻¹. The precision and accuracy of this method showed a great increase compared with traditional solid‐phase extraction. The developed method was successfully applied to extraction and analysis of NSAIDs in different water samples with satisfactory results which could help us better understand their environmental fate and risk to ecological health.     

Solid‐phase microextraction based on an agarose‐chitosan‐multiwalled carbon nanotube composite film combined with HPLC–UV for the determination of nonsteroidal anti‐inflammatory drugs in aqueous samples

We describe the preparation, characterization, and application of a composite film adsorbent based on blended agarose‐chitosan‐multiwalled carbon nanotubes for the preconcentration of selected nonsteroidal anti‐inflammatory drugs in aqueous samples before determination by high performance liquid chromatography with ultraviolet detection. The composite film showed a high surface area (4.0258 m²/g) and strong hydrogen bonding between the multiwalled carbon nanotubes and agarose/chitosan matrix, which prevent adsorbent deactivation and ensure long‐term stability. Several parameters, such as sample pH, addition of salt, extraction time, desorption solvent, and concentration of multiwalled carbon nanotubes in the composite film were optimized using a one‐factor‐at‐time approach. The optimum extraction conditions obtained were as follows: isopropanol as conditioning solvent, 10 mL of sample solution at pH 2, extraction time of 30 min, stirring speed of 600 rpm, 100 μL of isopropanol as desorption solvent, desorption time of 5 min under ultrasonication, and 0.4% w/v of composite film. Under the optimized conditions, the calibration curve showed good linearity in the range of 1–500 ng/mL (r² = 0.997–0.999), and good limits of detection (0.89–8.05 ng/mL) were obtained with good relative standard deviations of < 4.59% (n = 3) for the determination of naproxen, diclofenac sodium salt, and mefenamic acid drugs.     

Graphene nanoparticles as pseudostationary phase for the electrokinetic separation of nonsteroidal anti‐inflammatory drugs

The exceptional properties of graphene (G) were exploited here to facilitate capillary electrokinetic separations. Two types of commercially available G consisting of nanoparticles containing—one to three and—four to six G sheets, respectively, were compared for this purpose. Both proved effective in separating the arylpropyl derivatives of nonsteroidal anti‐inflammatory drugs. The highest resolution and shortest migration times were obtained with G containing high amount of single and double G nanosheets. G affords higher resolution than other types of nanoparticles; stable suspensions can be easily prepared and used as BGE without the need of adding an additional surfactant. This results in a high reproducibility in migration times and stability in background noise. The LOD and LOQ obtained by using G nanoparticles as pseudostationary phases spanned the range 0.29–1.18 mg/L and 0.95–3.95 mg/L, respectively, and the RSD was less than 4.7% in all instances.     

Clay‐Na as a sorbent for the extraction of anti‐inflammatory compounds in water samples

In this work, clay‐Na particles are used as the adsorbent for the solid‐phase extraction of acidic compounds. The novel sorbent under study is based on high‐specific surface area, cation‐exchange capacity designed specifically to offer ion‐exchange properties with the goal being to selectively extract a group of acidic compounds. The effects of the extraction parameters including extraction elution solvent, sample volume and pH. In optimum conditions, the repeatability for one fiber (n = 3), expressed as % relative standard deviation, was between 0.3 and 4.3% for the acid compounds. The detection limits for the studied acidic compounds were between 0.1–0.6 μg/L. The developed method offers the advantages of being simple to use and having a low cost of equipment.     

Facile preparation of magnetic graphene oxide/nanoscale zerovalent iron adsorbent for magnetic solid‐phase extraction of ultra‐trace quinolones in milk samples

A simple pH‐responsive magnetic solid‐phase extraction method was developed using graphene oxide–coated nanoscale zerovalent iron nanoparticles as an efficient adsorbent prior to high‐performance liquid chromatography‐tandem mass spectrometry for determination of ultra‐trace quinolones in milk samples. Various parameters affecting maghemite synthesis and separation such as pH of sample solution, amount of magnetic adsorbent, eluent type, and volume were optimized. The limits of detection are from 3.1 to 13.3 ng/L. The intra‐ and interprecision values are in the range of 2.9–6.9% and 7.6–15.1%, respectively. Recoveries are from 82.4 to 103.9%. Therefore, this simple and sensitive method is suitable for detecting ultra‐trace quinolone residues in milk.     

One‐pot synthesis of magnetic zeolitic imidazolate framework/grapheme oxide composites for the extraction of neonicotinoid insecticides from environmental water samples

Magnetic zeolitic imidazolate framework 67/graphene oxide composites were synthesized by one‐pot method at room temperature for the first time. Electrostatic interactions between positively charged metal ions and both negatively charged graphene oxide and Fe₃O₄ nanoparticles were expected to chemically stabilize magnetic composites to generate homogeneous magnetic products. The additional amount of graphene oxide and stirring time of graphene oxide, Co²⁺, and Fe₃O₄ solution were investigated. The zeolitic imidazolate framework 67 and Fe₃O₄ nanoparticles were uniformly attached on the surface of graphene oxide. The composites were applied to magnetic solid‐phase extraction of five neonicotinoid insecticides in environmental water samples. The main experimental parameters such as amount of added magnetic composites, extraction pH, ionic strength, and desorption solvent were optimized to increase the capacity of adsorbing neonicotinoid insecticides. The results show limits of detection at signal‐to‐noise ratio of 3 were 0.06–1.0 ng/mL under optimal conditions. All analytes exhibited good linearity with correlation coefficients of higher than 0.9915. The relative standard deviations for five neonicotinoid insecticides in environmental samples ranged from 1.8 to 16.5%, and good recoveries from 83.5 to 117.0% were obtained, indicating that magnetic zeolitic imidazolate framework 67/graphene oxide composites were feasible for analysis of trace analytes in environmental water samples.     

Magnetic solid‐phase extraction of tobacco‐specific N‐nitrosamines using magnetic graphene composite as sorbent

Tobacco‐specific N‐nitrosamines are carcinogenic components in mainstream cigarette smoke. To explore tobacco‐specific N‐nitrosamine release levels in cigarettes, a magnetic solid‐phase extraction procedure using magnetic graphene composite as sorbent for fast enrichment of tobacco‐specific N‐nitrosamine was developed. Under optimal conditions, a tobacco‐specific N‐nitrosamine determination method was successfully proposed by combining magnetic solid‐phase extraction procedure and high‐performance liquid chromatography coupled with tandem mass spectrometry. The method's limit of detection for tobacco‐specific N‐nitrosamines in mainstream cigarette smoke ranged from 0.018 to 0.057 ng/cigarette. Good linearities were obtained with correlation coefficients above 0.9992. The accuracies of tobacco‐specific N‐nitrosamines in a spiked mainstream cigarette smoke sample were from 89.3 to 109.4%, with a relative standard deviation of less than 11.2%. The proposed method has the merits of rapidity and high sensitivity. Finally, the method was successfully applied to tobacco‐specific N‐nitrosamine analysis in real samples.     

Capillary electrophoresis determination of nonsteroidal anti‐inflammatory drugs in wastewater using hollow fiber liquid‐phase microextraction

The presence of pharmaceuticals in the environment due to growing worldwide consumption has become an important problem that requires analytical solutions. This paper describes a CE determination for several nonsteroidal anti‐inflammatory drugs (ibuprofen, naproxen, ketoprofen, diclofenac, ketorolac, aceclofenac and salicylic acid) in environmental waters using hollow fiber membrane liquid‐phase microextraction. The extraction was carried out using a polypropylene membrane supporting dihexyl ether and the electrophoretic separation was performed in acetate buffer (30 mM, pH 4) using ACN as the organic modifier. Detection limits between 0.25 and 0.86 ng/mL were obtained, respectively. The method could be applied to the direct determination of the seven anti‐inflammatories in wastewaters, and five of them have been determined or detected in different urban wastewaters.     

Magnetic iron(III)‐based framework composites for the magnetic solid‐phase extraction of fungicides from environmental water samples

We adopted a facile hydrofluoric acid‐free hydro‐/solvothermal method for the preparation of four magnetic iron(III)‐based framework composites (MIL‐101@Fe₃O₄‐COOH, MIL‐101‐NH₂@Fe₃O₄‐COOH, MIL‐53@Fe₃O₄‐COOH, and MIL‐53‐NH₂@Fe₃O₄‐COOH). The obtained four magnetic iron(III)‐based framework composites were applied to magnetic separation and enrichment of the fungicides (prochloraz, myclobutanil, tebuconazole, and iprodione) from environmental samples before high‐performance liquid chromatographic analysis. MIL‐101‐NH₂@Fe₃O₄‐COOH showed more remarkable pre‐concentration ability for the fungicides as compared to the other three magnetic iron(III)‐based framework composites. The extraction parameters affecting enrichment efficiency including extraction time, sample pH, elution time, and the desorption solvent were investigated and optimized. Under the optimized conditions, the standard curve of correlation coefficients were all above 0.991, the limits of detection were 0.04–0.4 μg/L, and the relative standard deviations were below 10.2%. The recoveries of two real water samples ranged from 71.1–99.1% at the low spiking level (30 μg/L). Therefore, the MIL‐101‐NH₂@Fe₃O₄‐COOH composites are attractive for the rapid and efficient extraction of fungicides from environmental water samples.     

Magnetic porous carbon derived from Co‐doped metal–organic frameworks for the magnetic solid‐phase extraction of endocrine disrupting chemicals

Metal–organic frameworks‐5 (MOF‐5) was explored as a template to prepare porous carbon due to its high surface area, large pore volume, and permanent nanoscale porosity. Magnetic porous carbon, Co@MOF‐5‐C, was fabricated by the one‐step direct carbonization of Co‐doped MOF‐5. After carbonization, the magnetic cobalt nanoparticles are well dispersed in the porous carbon matrix, and Co@MOF‐5‐C displays strong magnetism (with the saturation magnetization intensity of 70.17emu/g), high‐specific surface area, and large pore volume. To evaluate its extraction performance, the Co@MOF‐5‐C was applied as an adsorbent for the magnetic solid‐phase extraction of endocrine disrupting chemicals, followed by their analysis with high‐performance liquid chromatography. The developed method exhibits a good linear response in the range of 0.5–100 ng/mL for pond water and 1.0–100 ng/mL for juice samples. The limits of detection (S/N  = 3) for the analytes were in the range of 0.1–0.2 ng/mL.     

Aminosilanized magnetic carbon microspheres for the magnetic solid‐phase extraction of bisphenol A,bisphenol AF,and tetrabromobisphenol A from environmental water samples

Aminosilanized magnetic carbon microspheres as a novel adsorbent were designed and fabricated. The adsorbent was used for the magnetic solid‐phase extraction of bisphenols at trace levels from environmental water samples before liquid chromatography with tandem mass spectrometry analysis. The structure, surface, and magnetic behavior of the as‐prepared aminosilanized magnetic carbon microspheres were characterized by elemental analysis, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, powder X‐ray diffraction, and vibrating sample magnetometry. The effects of the experimental parameters were investigated by the Plackett–Burman design, and then the parameters that were significant to the extraction efficiencies were optimized through a response surface methodology. The aminosilanized magnetic carbon microspheres exhibited high adsorption efficiency and selectivity for bisphenols. Under optimal conditions, low limits of detection (0.011–2.22 ng/L), and a wide linear range (2–3 orders of magnitude), good repeatability (4.7–7.8%, n = 5), and reproducibility (6.0–8.3%, n = 3) were achieved. The results demonstrate that the novel adsorbent possesses great potentials in the determination of trace levels of bisphenols in environmental water samples.     

Pipette‐tip solid‐phase extraction based on deep eutectic solvent modified graphene for the determination of sulfamerazine in river water

A green and novel deep eutectic solvent modified graphene was prepared and used as a neutral adsorbent for the rapid determination of sulfamerazine in a river water sample by pipette‐tip solid‐phase extraction. Compared with conventional graphene, deep eutectic solvent modified graphene can change the surface of graphene with wrinkled structure and higher selective extraction ability. The properties of deep eutectic solvent modified graphene and graphene were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Static adsorption showed deep eutectic solvent modified graphene had a higher adsorption ability (18.62 mg/g) than graphene. Under the optimum conditions, factors such as kinds of washing solvents and elution solvents and volume of elution solvent were evaluated. The limits of detection and quantification were 0.01 and 0.03 μg/mL, respectively. The method recoveries of sulfamerazine were in the range of 91.01–96.82% with associated intraday relative standard deviations ranging from 1.63 to 3.46% and interday relative standard deviations ranging from 0.68 to 3.84%. Deep eutectic solvent modified graphene showed satisfactory results (recovery was 95.38%) and potential for rapid purification of sulfamerazine in river water sample in combination with the pipette‐tip solid‐phase extraction method.     

Determination of trace amounts of aromatic amines after magnetic solid‐phase extraction using silver‐modified Fe3O4/graphene nanocomposite

In this work, a fast and simple magnetic dispersive solid phase extraction methodology was developed utilizing Ag@magnetite nanoparticles@graphene nanocomposite as an efficient magnetic nanosorbent for preconcentration and determine of five aromatic amines in water samples. The sorbent was characterized by diverse characterization techniques. After the extraction, high‐performance liquid chromatography with UV detection was utilized to analysis the aromatic amines. The effects of different factors on the extraction process were studied thoroughly via design of experiment and desirability function. Detection limits and linear dynamic ranges were obtained in the range of 0.10–0.20 and 0.3–300 μg/L, respectively. The relative standard deviations (n = 5) were in the range of 4.3–6.5%. Eventually, the method was employed for determination of target aromatic amines in various water samples.     

Loading controlled magnetic carbon dots for microwave‐assisted solid‐phase extraction: Preparation,extraction evaluation and applications in environmental aqueous samples

An adsorbent of carbon dot@poly(glycidyl methacrylate)@Fe₃O₄ nanoparticles has been developed for the microwave‐assisted magnetic solid‐phase extraction of polycyclic aromatic hydrocarbons in environmental aqueous samples prior to high‐performance liquid chromatography with UV/visible spectroscopy detection. Poly(glycidyl methacrylate) was synthesized by atom transfer radical polymerization. The chain length and amount of carbon dots attached on them can be easily controlled through changing polymerization conditions, which contributes to tunable extraction performance. The successful fabrication of the nano‐adsorbent was confirmed by transmission electronic microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and vibrating sample magnetometry. The extraction performance of the adsorbent was evaluated by using polycyclic aromatic hydrocarbons as model analytes. The key factors influencing the extraction, such as microwave power, adsorption time, desorption time and desorption solvents were investigated in detail. Under the optimal conditions, the microwave‐assisted method afforded magnetic solid‐phase extraction with short extraction time, wide dynamic linear range (0.02–200 μg/L), good linearity (R² ≥ 98.57%) and low detection limits (20–90 ng/L) for model analytes. The adsorbent was successfully applied for analyzing polycyclic aromatic hydrocarbons in environmental aqueous samples and the recoveries were in the range of 86.0–124.2%. Thus, the proposed method is a promising candidate for fast and reliable preconcentration of trace polycyclic aromatic hydrocarbons in real water samples.     

Magnetic graphene oxide modified by imidazole‐based ionic liquids for the magnetic‐based solid‐phase extraction of polysaccharides from brown alga

Magnetic graphene oxide was modified by four imidazole‐based ionic liquids to synthesize materials for the extraction of polysaccharides by magnetic solid‐phase extraction. Fucoidan and laminarin were chosen as the representative polysaccharides owing to their excellent pharmaceutical value and availability. Fourier transform infrared spectroscopy, field‐emission scanning electron microscopy, and thermogravimetric analysis were applied to characterize the synthesized materials. Single‐factor experiments showed that the extraction efficiency of polysaccharides was affected by the amount of ionic liquids for modification, solid–liquid ratio of brown alga and ethanol, the stirring time of brown alga and ionic liquid‐modified magnetic graphene oxide materials, and amount of 1‐(3‐aminopropyl)imidazole chloride modified magnetic graphene oxide materials added to the brown alga sample solution. The results indicated that 1‐(3‐aminopropyl)imidazole chloride modified magnetic graphene oxide possessed better extraction ability than graphene oxide, magnetic graphene oxide, and other three ionic‐liquid‐modified magnetic graphene oxide materials. The highest extraction recoveries of fucoidan and laminarin extracted by 1‐(3‐aminopropyl)imidazole chloride modified magnetic graphene oxide were 93.3 and 87.2%, respectively. In addition, solid materials could be separated and reused easily owing to their magnetic properties.     

Magnetic nanocomposite of self‐doped polyaniline–graphene as a novel sorbent for solid‐phase extraction

This work is the first study on the extraction efficiency of self‐doped polyaniline that is immobilized on the graphene‐modified magnetic nanoparticles. The new material was used as a sorbent for the magnetic solid‐phase extraction of methyl‐, propyl‐, and butylparabens. The use of graphene provides a high surface area and prevents aggregation of the nanoparticles. The self‐doped polyaniline also provides multifunctionality, high extraction capacity, and chemical stability even in the basic medium. The parabens were acetylated for determination by gas chromatography with flame ionization detection. The effects of monomer ratio, extraction solvent, sorbent amount, sample volume, desorption solvent volume, adsorption and desorption times, and sample ionic strength were optimized. Preconcentration factors obtained were from 190 to 310. The detection limits of the method were <2.8 μg/L. Linear ranges of the method were 5–2000 μg/L for propyl and butyl parabens, and 10–2000 μg/L for methyl paraben. The method was applied for the determination of the parabens in cosmetic products and extraction recoveries were 89–101% with RSDs ≤7.9%.     

Single‐drop microextraction combined in‐line with capillary electrophoresis for the determination of nonsteroidal anti‐inflammatory drugs in urine samples

This study describes a method to determine nonsteroidal anti‐inflammatory drugs (NSAIDs) in urine samples based on the use of single‐drop microextraction (SDME) in a three‐phase design as a preconcentration technique coupled in‐line to capillary electrophoresis. Different parameters affecting the extraction efficiency of the SDME process were evaluated (e.g. type of extractant, volume of the microdroplet, and extraction time). The developed method was successfully applied to the analysis of human urine samples with LODs ranging between 1.0 and 2.5 μg/mL for all of the NSAIDs under study. This method shows RSD values ranging from 8.5 to 15.3% in interday analysis. The enrichment factors were calculated, resulting 27‐fold for ketoprofen, 14‐fold for diclofenac, 12‐fold for ibuprofen, and 44‐fold naproxen. Samples were analyzed applying the SDME–CE method and the obtained results presented satisfactory recovery values (82–115%). The overall method can be considered a promising approach for the analysis of NSAIDs in urine samples after minimal sample pretreatment.