Development of a new strategy for the synthesis of graphene oxide-alumina nanocomposite as an efficient adsorbent for dispersive solid-phase extraction of parabens

The present study investigates the synthesis and application of the graphene oxide-alumina nanocomposite as a new adsorbent for the dispersive solid-phase extraction of three parabens and their determination using high-performance liquid chromatography-ultraviolet detection. The characterization of the synthesized material was accomplished and its size, morphology, chemical composition, porosity, and thermal stability were studied. Application of the proposed strategy for the synthesis of the nanocomposite resulted in the incorporation of Al₂O₃ nanoparticles into graphene oxide nanosheets, further resulting in the exfoliation of graphene oxide nanosheets increasing their surface area. An orthogonal rotatable central composite design was used to optimize the extraction. Under the optimum conditions, the analytical performance of the method showed a suitable linear dynamic range (0.2–100.0 μg/L), reasonable limits of detection (0.03–0.05 μg/L), and preconcentration factors ranging from 128 to 173. Finally, the new validated method was applied for the determination of parabens in some real samples including wastewater, cream, toothpaste, and juice samples with satisfactory recoveries (88%–109%), and relative standard deviations less than 8.7% (n = 3). Results demonstrated that inserting alumina nanoparticles into graphene oxide nanosheets improved the extraction efficiency of parabens, as polar acidic compounds, by providing additional efficient interactions including hydrogen bonding, dipole-dipole, and Brønsted and Lewis acid-base interactions.     

Metal-organic framework derived magnetic nanoporous carbon as an adsorbent for the magnetic solid-phase extraction of chlorophenols from mushroom sample

In this work, a metal-organic framework derived nanoporous carbon(MOF-5-C) was fabricated and modified with Fe_3O_4 magnetic nanoparticles. The resulting magnetic MOF-5-derived porous carbon(Fe_3O_4@MOF-5-C) was then used for the magnetic solid-phase extraction of chlorophenols(CPs) from mushroom samples prior to high performance liquid chromatography–ultraviolet detection. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and N_2 adsorption were used to characterize the adsorbent. After experimental optimization, the amount of the adsorbent was chosen as 8.0 mg, extraction time as 10 min, sample volume as 50 m L, desorption solvent as 0.4 m L(0.2 mL×2)of alkaline methanol, and sample p H as 6. Under the above optimized conditions, good linearity for the analytes was obtained in the range of 0.8–100.0 ng g~(-1)with the correlation coefficients between0.9923 and 0.9963. The limits of detection(S/N = 3) were in the range of 0.25–0.30 ng g~(-1), and the relative standard deviations were below 6.8%. The result showed that the Fe3O4@MOF-5-C has an excellent adsorption capacity for the analytes.     

In-situ sorbent formation for the extraction of pesticides from honey

An organic polymer was re-precipitated in solution to use as an adsorbent in dispersive solid-phase extraction of some pesticides from honey samples prior to their determination by high-performance liquid chromatography-tandem mass spectrometry. In this approach, different deep eutectic solvents were prepared using lysine and their ability in elution of the analytes from the adsorbent surface was tested. A diluted honey solution was transferred into a glass test tube and then a solution of polystyrene dissolved in dimethylformamide was injected into the solution. By doing this, polystyrene is re-precipitated in the solution and dispersed in whole parts of it as many tiny particles. Then the mixture was centrifuged and the adsorbed analytes on the particles were eluted using a proper hydrophilic deep eutectic solvent. The central composite design approach was used for the optimization of effective parameters. The limits of detection and quantification were in the ranges of 0.06–0.20 and 0.22–0.69 ng/g, respectively. The calibration curves obtained by matrix-matched standard solutions were linear in the range of 0.69–500 ng/g with a coefficient of determinations ≥0.9962. The method provided high extraction recoveries (70–99%) and enrichment factors (140–198), and an acceptable precision (relative standard deviations ≤7.1%).     

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, Fe₃O₄ 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.     

Magnetic polyethyleneimine functionalized reduced graphene oxide as a novel magnetic solid-phase extraction adsorbent for the determination of polar acidic herbicides in rice

A novel magnetic polyethyleneimine modified reduced graphene oxide (Fe₃O₄@PEI-RGO) had been fabricated based on a self-assemble approach between positive charged magnetic polyethyleneimine (Fe₃O₄@PEI) and negative charged GO sheets via electrostatic interaction followed by chemical reduction of GO to RGO. The as-prepared Fe₃O₄@PEI-RGO was characterized by transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FT-IR), X-ray diffraction (XRD), thermal gravimetric analyzer (TGA), vibrating sample magnetometer (VSM) and zeta potential analysis, and then was successfully applied to determine four phenoxy acid herbicides and dicamba in rice coupled with high performance liquid chromatography (HPLC). As a surface modifier of RGO, PEI not only effectually affected the surface property of RGO (e.g. zeta potential), but also changed the polarity of RGO and offered anion exchange groups to polar acidic herbicides, which would directly influence the type of adsorbed analytes. Compared with Fe₃O₄@PEI, Fe₃O₄/RGO and Fe₃O₄@PEI-GO, the as-prepared Fe₃O₄@PEI-RGO, integrating the superiority of PEI and RGO, showed higher extraction efficiency for polar acidic herbicides. Besides, the adsorption mechanism was investigated as well. It turned out that electrostatic interaction and π-π interaction were considered to be two major driving force for the adsorption process. Response surface methodology (RSM), a multivariate experimental design technique, was used to optimize experimental parameters affecting the extraction efficiency in detail. Under the optimal conditions, a satisfactory performance was obtained. The calibration curves were linear over the concentration ranging from 2 to 300 ng g⁻¹ with correlation coefficients (r) between 0.9985 and 0.9994. The limits of detection (LODs) were in the range of 0.67–2 ng g⁻¹. The recoveries ranged from 87.41% to 102.52% with relative standard deviations (RSDs) less than 8.94%. Taken together, the proposed method was an efficient pretreatment and enrichment procedure and could be successfully applied for selective extraction and determination of polar acidic herbicides in complex matrices.     

石墨烯应用于样品前处理的研究进展

样品前处理技术在样品分析中发挥着越来越重要的作用,而对分析物的富集能力和对样品基体的净化程度主要取决于高效的样品前处理材料,所以发展高性能的样品前处理材料一直是该领域的前沿研究方向。近年来,各类先进材料已经被引入样品前处理领域,发展了多种高性能的萃取材料。由于独特的物理化学性质,石墨烯已在各个研究领域获得广泛关注,在样品前处理领域也发挥着重要作用。基于高的比表面积、大的π电子结构、优异的吸附性能、丰富的官能团和易于化学改性等优点,石墨烯和氧化石墨烯基萃取材料被成功应用于各种样品的前处理,对不同领域中多种类型分析物表现出优异的萃取性能。该论文总结和讨论了近3年来石墨烯材料(石墨烯、氧化石墨烯及其功能化材料)在柱固相萃取、分散固相萃取、磁性固相萃取、搅拌棒萃取、纤维固相微萃取和管内固相微萃取等方面的研究进展。基于多种萃取机理如π-π、静电、疏水、亲水、氢键等相互作用,石墨烯萃取材料能够高效萃取和选择性富集不同类别的目标分析物,如重金属离子、多环芳烃、塑化剂、雌激素、药物分子、农药残留、兽药残留等。基于新型石墨烯萃取材料的各种样品前处理技术与多种检测技术如色谱、质谱、原子吸收光谱等联用,广泛应用于环境监测、食品安全和生化分析等领域。最后,总结了石墨烯在样品前处理领域中存在的问题,并展望了未来的发展趋势。     

The use of graphene-based magnetic nanoparticles as adsorbent for the extraction of triazole fungicides from environmental water

A graphene-based magnetic nanocomposite (graphene-ferriferrous oxide; G-Fe(3) O(4) ) was synthesized and used as an effective adsorbent for the preconcentration of some triazole fungicides (myclobutanil, tebuconazole, and hexaconazole) in environmental water samples prior to high-performance liquid chromatography-ultraviolet detection. The method, which takes the advantages of both nanoparticle adsorption and magnetic phase separation from the sample solution, could avoid the time-consuming experimental procedures commonly involved in the traditional solid phase extraction such as centrifugation and filtrations. Various experimental parameters affecting the extraction efficiencies such as the amount of the magnetic nanocomposite, extraction time, the pH values of the sample solution, salt concentration, and desorption conditions were investigated. Under the optimum conditions, the enrichment factors of the method for the three analytes were 5824, 3600, and 4761, respectively. A good linearity was observed in the range of 0.1-50 ng/mL for tebuconazole and 0.05-50 ng/mL for myclobutanil and hexaconazole, respectively, with the correlation coefficients ranging from 0.9992 to 0.9996. The limits of detection (S/N = 3) of the method were between 0.005 and 0.01 ng/mL. The results indicated that as a magnetic solid-phase extraction adsorbent, the graphene-ferriferrous oxide (G-Fe(3) O(4) ) has a great potential for the preconcentration of some compounds from liquid samples.     

Determination of trace hydroxyl polycyclic aromatic hydrocarbons in urine using graphene oxide incorporated monolith solid‐phase extraction coupled with LC‐MS/MS

The biomonitoring of hydroxy polycyclic aromatic hydrocarbons in urine, as a direct way to access multiple exposures to polycyclic aromatic hydrocarbons, has raised great concerns due to their increasing hazardous health effects on humans. Solid‐phase extraction is an effective and useful technique to preconcentrate trace analytes from biological samples. Here, we report a novel solid‐phase extraction method using a graphene oxide incorporated monolithic syringe for the determination of six hydroxy polycyclic aromatic hydrocarbons in urine coupled with liquid chromatography‐tandem mass spectrometry. The effect of graphene oxide amount, washing solvent, eluting solvent, and its volume on the extraction performance were investigated. The fabricated monoliths gave higher adsorption efficiency and capacity than the neat polymer monolith and commercial C₁₈ sorbent. Under the optimum conditions, the developed method provided the detection limits (S/N = 3) of 0.02–0.1 ng/mL and the linear ranges of 0.1–1500 ng/mL for six analytes in urine sample. The recoveries at three spiked levels ranged from 77.5 to 97.1%. Besides, the intra column‐to‐column (n = 3) and inter batch‐to‐batch (n = 3) precisions were ≤ 9.8%. The developed method was successfully applied for the determination of hydroxy polycyclic aromatic hydrocarbons in urine samples of coke oven workers.     

Preparation of magnetic chitosan and graphene oxide-functional guanidinium ionic liquid composite for the solid-phase extraction of protein

A series of novel cationic functional hexaalkylguanidinium ionic liquids and anionic functional tetraalkylguanidinium ionic liquids have been synthesized, and then magnetic chitosan graphene oxide (MCGO) composite has been prepared and coated with these functional guanidinium ionic liquids to extract protein by magnetic solid-phase extraction. MCGO-functional guanidinium ionic liquid has been characterized by vibrating sample magnetometer, field emission scanning electron microscopy, X-ray diffraction spectrometer and Fourier transform infrared spectrometer. After extraction, the concentrations of protein were determined by measuring the absorbance at 278 nm using an ultra violet visible spectrophotometer. The advantages of MCGO-functional guanidinium ionic liquid in protein extraction were compared with magnetic chitosan, graphene oxide, MCGO and MCGO-ordinary imidazolium ionic liquid. The proposed method has been applied to extract trypsin, lysozyme, ovalbumin and bovine serum albumin. A comprehensive study of the adsorption conditions such as the concentration of protein, the amount of MCGO-functional guanidinium ionic liquid, the pH, the temperature and the extraction time were also presented. Moreover, the MCGO-functional guanidinium ionic liquid can be easily regenerated, and the extraction capacity was about 94% of the initial one after being used three times.     

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.     

Sensitive determination of probenecid in urine samples by reversed-phase liquid chromatography and UV-visible detection using solid-phase extraction techniques for sample clean-up

Summary This study describes a rapid method for the determination of probenecid in human urine by liquid chromatography with UV detection at 254 nm, after clean-up through a C8 solid-phase extraction column. Liquid chromatography was carried out on a C18-bonded phase using an acetonitrile-acetate buffer (pH=4) gradient elution. Ethacrynic acid was used as internal standard. The system has been applied to the determination of probenecid in the 0.10–100.0 g/ml concentration range; the limit of detection was 5 ng/mL.     

Development of a novel mixed hemimicelles dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene for the separation and preconcentration of fluoxetine in different matrices before its determination by fiber optic linear array spectrophotometry and mode-mismatched thermal lens spectroscopy

This study aims at developing a novel, sensitive, fast, simple and convenient method for separation and preconcentration of trace amounts of fluoxetine before its spectrophotometric determination. The method is based on combination of magnetic mixed hemimicelles solid phase extraction and dispersive micro solid phase extraction using 1-hexadecyl-3-methylimidazolium bromide coated magnetic graphene as a sorbent. The magnetic graphene was synthesized by a simple coprecipitation method and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). The retained analyte was eluted using a 100 μL mixture of methanol/acetic acid (9:1) and converted into fluoxetine-β-cyclodextrin inclusion complex. The analyte was then quantified by fiber optic linear array spectrophotometry as well as mode-mismatched thermal lens spectroscopy (TLS). The factors affecting the separation, preconcentration and determination of fluoxetine were investigated and optimized. With a 50 mL sample and under optimized conditions using the spectrophotometry technique, the method exhibited a linear dynamic range of 0.4–60.0 μg L⁻¹, a detection limit of 0.21 μg L⁻¹, an enrichment factor of 167, and a relative standard deviation of 2.1% and 3.8% (n = 6) at 60 μg L⁻¹ level of fluoxetine for intra- and inter-day analyses, respectively. However, with thermal lens spectrometry and a sample volume of 10 mL, the method exhibited a linear dynamic range of 0.05–300 μg L⁻¹, a detection limit of 0.016 μg L⁻¹ and a relative standard deviation of 3.8% and 5.6% (n = 6) at 60 μg L⁻¹ level of fluoxetine for intra- and inter-day analyses, respectively. The method was successfully applied to determine fluoxetine in pharmaceutical formulation, human urine and environmental water samples.     

Magnetic porous carbon derived from a metal–organic framework as a magnetic solid‐phase extraction adsorbent for the extraction of sex hormones from water and human urine

An iron‐embedded porous carbon material (MIL‐53‐C) was fabricated by the direct carbonization of MIL‐53. The MIL‐53‐C possesses a high surface area and good magnetic behavior. The structure, morphology, magnetic property, and porosity of the MIL‐53‐C were studied by scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, and N₂ adsorption. With the use of MIL‐53‐C as the magnetic solid‐phase extraction adsorbent, a simple and efficient method was developed for the magnetic solid‐phase extraction of three hormones from water and human urine samples before high‐performance liquid chromatography with UV detection. The developed method exhibits a good linear response in the range of 0.02–100 ng/mL for water and 0.5–100 ng/mL for human urine samples , respectively. The limit of detection (S/N = 3) for the analytes was 0.005–0.01 ng/mL for water sample and 0.1–0.3 ng/mL for human urine sample. The limit of quantification (S/N = 10) of the analytes were in the range of 0.015–0.030 and 0.3–0.9 ng/mL, respectively.     

Magnetic spherical carbon as an efficient adsorbent for the magnetic extraction of phthalate esters from lake water and milk samples

Magnetic spherical carbon was synthesized by a facile hydrothermal carbonization procedure with biomass glucose as the carbon precursor and nanoclusters iron colloid as magnetic precursor. The textures of the as‐prepared magnetic spherical carbon were characterized by nitrogen adsorption–desorption isotherms, X‐ray diffraction, transmission electron microscopy, scanning electron microscopy and vibration sample magnetometry. Results indicated that the magnetic spherical carbon possessed high surface area as well as strong magnetism, which endows the material with good adsorption capability and easy separation properties. To assess its absorption performance, the magnetic spherical carbon was employed as adsorbent for the extraction and preconcentration of phthalate esters from lake water and milk samples before high‐performance liquid chromatographic analysis. Some key parameters that could influence the enrichment efficiency were investigated. Under the optimum conditions, a good linearity was achieved with the linear correlation coefficients higher than 0.9973. The limits of detection (S/N = 3) were 0.05–0.08 ng/mL for lake water and 0.1–0.2 ng/mL for milk samples. The recoveries of the analytes for the method were in the range 80.1–112.6%.     

Evaluation of graphene as an advantageous adsorbent for solid-phase extraction with chlorophenols as model analytes

Graphene, a novel class of carbon nanostructures, possesses an ultrahigh specific surface area, and thus has great potentials for the use as sorbent materials. We herein demonstrate the use of graphene as a novel adsorbent for solid-phase extraction (SPE). Eight chlorophenols (CPs) as model analytes were extracted on a graphene-packed SPE cartridge, and then eluted with alkaline methanol. The concentrations in the eluate were determined by HPLC with multi-wavelength UV detection. Under the optimized conditions, high sensitivity (detection limits 0.1-0.4 ng/mL) and good reproducibility of CPs (RSDs 2.2-7.7% for run-to-run assays) were achieved. Comparative studies showed that graphene was superior to other adsorbents including C18 silica, graphitic carbon, single- and multi-walled carbon nanotubes for the extraction of CPs. Some other advantages of graphene as SPE adsorbent, such as good compatibility with various organic solvents, good reusability and no impact of sorbent drying, have also been demonstrated. The proposed method was successfully applied to the analysis of tap and river water samples with recoveries ranging from 77.2 to 116.6%. This work not only proposes a useful method for environmental water sample pretreatment, but also reveals great potentials of graphene as an excellent sorbent material in analytical processes.     

Polyamide as an efficient sorbent for simultaneous interference-free determination of three Sudan dyes in saffron and urine using high-performance liquid chromatography-ultra violet detection北大核心CSCD

With polyamide( PA)as an efficient sorbent for solid phase extraction( SPE)of Sudan dyes II,III and Red 7B from saffron and urine,their determination by HPLC was performed. The optimum conditions for SPE were achieved using 7 mL methanol/water( 1:9,v/v,pH 7)as the washing solvent and 3 mL tetrahydrofu-ran for elution. Good clean-up and high( above 90%)recoveries were observed for all the analytes. The opti-mized mobile phase composition for HPLC analysis of these compounds was methanol-water( 70:30,v/v). The SPE parameters,such as the maximum loading capacity and breakthrough volume,were also determined for each analyte. The limits of detection( LODs),limits of quantification( LOQs),linear ranges and recoveries for the analytes were 4. 6-6. 6 μg/L,13. 0-19. 8 μg/L,13. 0-5 000 μg/L( r2> 0. 99)and 92. 5% -113. 4%,respec-tively. The precisions( RSDs)of the overall analytical procedure,estimated by five replicate measurements for Sudan II,III and Red 7B in saffron and urine samples were 2. 3%,1. 8% and 3. 6%,respectively. The developed method is simple and successful in the application to the determination of Sudan dyes in saffron and urine sam-ples with HPLC coupled with UV detection.     

Electrospun polystyrene nanofibers as a novel adsorbent to transfer an organic phase from an aqueous phase

The aim of this work is to develop a simple phase‐transfer method for dispersive liquid–liquid microextraction. For this purpose, a polystyrene nanofiber was prepared by a facile electrospinning strategy and used for the first time as an adsorbent to transfer the organic phase in dispersive liquid–liquid microextraction procedure. The fiber was characterized and its chemical stability and excellent hydrophobicity enable it to selectively adsorb the organic solvent in an aqueous sample. High porosity and specific surface area provide a large adsorption capacity. Under the optimal conditions, the developed dispersive liquid–liquid microextraction with high‐performance liquid chromatography method was successfully applied to the analysis of aldehydes in environmental water samples. The merits of this approach are that it is easy‐to‐operate, low‐cost, time‐saving, and has satisfactory sensitivity. It provides an alternative way for fast and convenient phase transfer of the hydrophobic organic solvent from the aqueous phase.     

Determination of Pesticide Residues in Fruit and Vegetables by High-Performance Liquid Chromatography–Tandem Mass Spectrometry with Multivariate Response Surface Methodology

Multivariate response surface methodology optimization using Placket–Burman and Box–Behnken designs were respectively used for the screening and optimization of significant factors for liquid chromatography–tandem mass spectrometry. Consequently, the optimized instrument successfully improved the sample preparation protocol and the method was validated. However, modified QuEChERS dispersive solid phase extraction coupled with ionic liquid-based dispersive liquid–liquid microextraction were used for the determination of multi-pesticide residues in fruit and vegetable samples. The analysed samples were jackfruit, strawberries, cucumber, pears, and carrots. The resulting linearity range (5–400?µg/kg) and regression coefficient (>0.99) results were satisfactory. The 94.2 and 95.8% accuracy (89–138%) and precision (0–25%) results were satisfactory and within the recommended ranges (≤20%) and (70–120%), respectively. The limits of detection (0.01–0.54?µg/kg) and quantitation (0.03–1.79?µg/kg) were excellent. The matrix effects (≤?87%) for all analysed samples were not significant. The estimated measurement uncertainties (≤27%) were within the acceptable range (≤50%). Justifiably, the response surface methodology optimized instrument and sample treatment techniques were reliable and convenient for multi-pesticide residue determination in various fruits and vegetables.     

Microwave‐assisted preparation of magnetic nanoparticles modified with graphene oxide for the extraction and analysis of phenolic compounds

Here in, magnetic nanoparticles combined with graphene oxide adsorbent were fabricated via a microwave‐assisted synthesis method, and used in the solid‐phase extraction of three phenolic compounds (phenol, 4‐nitrophenol, and m‐methylphenol) in environmental water samples. Various instrumental methods were employed to characterize the magnetic nanoparticles modified with graphene oxide. The influence of experimental parameters, such as desorption conditions, amount of adsorbent, extraction time, and pH, on the extraction efficiency was investigated. Owing to the high surface area and excellent adsorption capacity of the prepared material, satisfactory extraction was achieved. Under optimum conditions, a linear response was observed in the concentration range of 1.000–100.0 μg/L for phenol, 0.996–99.6 μg/L for 4‐nitrophenol, and 0.975–97.5 μg/L for m‐methylphenol, with correlation coefficients in the range of 0.9995–0.9997. The limit of detection (signal‐to‐noise ratio of 3) of the method varied between 0.5 and 0.8 μg/L. The relative standard deviations were <5.2%. The recovery percentages of the method were in the range of 89.1–104.3%. The results indicate that the graphene oxide‐modified magnetic nanoparticles possess high adsorptive abilities toward phenolic compounds in environmental water samples.     

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.