Boronate affinity adsorption of cis‐diol‐containing biomolecules in nonaqueous solvent

Boronate affinity has attracted much attention in recent years. It has been broadly used for selective isolation and enrichment of cis‐diol‐containing molecules. Conventionally, the cis‐diols are adsorbed in mild alkaline aqueous solutions. In this work, for the first time, we found that boronate affinity adsorption could also be performed in nonaqueous solvent at nonbasic pH. Cis‐diol‐containing compounds present in herbal medicines were used for the adsorption test. The results indicated that all compounds obtained higher recoveries in the organic solvents (methanol, acetonitrile, ethyl acetate) compared with alkaline buffer. The adsorption of vicinal cis‐diol‐containing molecules in organic solvents could be accomplished rapidly, with high selectivity and high recoveries (>80%). These results shed light on the possibility of boronate affinity adsorption in nonaqueous solvents. The results are very important for the isolation and enrichment of cis‐diols, which have poor solubility in water, especially for those in herbal medicines. Copyright © 2015 John Wiley & Sons, Ltd.     

Fabrication of boronate‐decorated polyhedral oligomeric silsesquioxanes grafted cotton fiber for the selective enrichment of nucleosides in urine

Various cotton fiber based boronate‐affinity adsorbents are recently developed for the sample pretreatment of cis‐diol‐containing biomolecules, but most do not have efficient capacity due to limited binding sites on the surface of cotton fibers. To increase the density of boronate groups on the surface of cotton fiber, polyhedral oligomeric silsesquioxanes were used to modify cotton fiber to provide plentiful reactive sites for subsequent functionalization with 4‐formylphenylboronic acid. The new adsorbent showed special recognition ability towards cis‐diols and high adsorption capacity (175 μg/g for catechol, 250 μg/g for dopamine, 400 μg/g for adenosine). The in‐pipette‐tip solid‐phase extraction was investigated under different conditions, including pH and ionic strength of solution, adsorbent amount, pipette times, washing solvent, and elution solvent. The in‐pipette‐tip solid‐phase extraction coupled with high‐performance liquid chromatography was used to analyze four nucleosides in urine samples. Under the optimal extraction conditions, the detection limits were determined to be between 5.1 and 6.1 ng/mL (S/N  =  3), and the linearity ranged from 20 to 500 ng/mL for these analytes. The accuracy of the analytical method was examined by studying the relative recoveries of analytes in real urine samples with recoveries varying from 83 to 104% (RSD = 3.9–10.2%, n = 3).     

Borated Titania,a New Option for the Selective Enrichment of cis‐Diol Biomolecules

As low abundance cis‐diol biomolecules are of great significance in biological organisms, preparation of materials for the selective enrichment of such compounds is highly favorable for the development of the related proteomics and metabolomics. To this end, we have prepared monolithic borated titania by a non‐aqueous sol‐gel strategy as a new inorganic affinity material for the specific capture of nucleosides, glycopeptides and glycoproteins. Benefiting from the inorganic framework, this material prevented the hydrophobic interference, which was somewhat inevitable for the mainstream organic‐based boronate affinity materials. The prepared material was carefully characterized by scanning electron microscope (SEM), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS) and nitrogen‐sorption experiments to investigate the morphology and elemental composition. The excellent performance of borated titania on enrichment of cis‐diol biomolecules was demonstrated by extracting the glycopeptides from horseradish peroxidase (HRP) digestion, standard glycoproteins, and nucleosides from a human‐urine matrix. This kind of inorganic affinity material offers a new option for selective enrichment or separation of cis‐diol biomolecules.     

The preparation of high-capacity boronate affinity adsorbents by surface initiated reversible addition fragmentation chain transfer polymerization for the enrichment of ribonucleosides in serum

Boronate affinity adsorption is uniquely selective for cis-diol-containing molecules. The preparation and application of boronate affinity materials has attracted much attention in recent years. In this work, a high-capacity boronate affinity adsorbent was prepared by surface-initiated reversible addition–fragmentation chain transfer polymerization (SI-RAFT). Commercial aminated poly(glycidyl methacrylate) (PGMA) microspheres were modified with the chain transfer agent (CTA) S-1-dodecyl-S-(α,α-dimethyl-α-acetic acid)trithiocarbonate (DDATC). Boronate-affinity adsorbents were then prepared via SI-RAFT polymerization employing 3-acrylamidophenylboronic acid (AAPBA) as the monomer. The Fourier transform infrared spectroscopy (FT-IR), nitrogen adsorption and desorption measurements have proven the successful grafting of AAPBA on PGMA microspheres surface. The boronate affinity adsorbents thus prepared possess much higher adsorption capacity (99.2 µmol/g of adenosine) and both faster adsorption and desorption speed towards ribonucleosides, the adsorption and desorption could be completed in 2 min. The high selectivity of the adsorbents to ribonucleosides was verified in the presence of a large excess of deoxynucleosides. The boronate affinity adsorbents were then employed for sample pretreatment before HPLC analysis of ribonucleosides in serum. The ribonucleosides were effectively enriched by boronate affinity dispersive solid-phase extraction (BA-DSPE), with high mass recoveries and good precision. The simultaneous determination of uridine and guanosine in calf serum was achieved by utilizing the standard addition method, their contents were determined to be 170 ± 11.6 ng/mL and 39.6 ± 4.4 ng/mL respectively. The results proved that the prepared boronate affinity materials could be applied for sample pretreatment of cis-diol containing molecules in biological samples.     

Enrichment of adenosine using thermally responsive chromatographic materials under friendly pH conditions

A thermally responsive boronate affinity chromatographic material, which showed thermal sensitivity, had been successfully applied for the enrichment and separation of cis‐diol‐containing compounds, and the capture and release process could be facilitated by adjusting the temperature. However, in this system, the pH of the mobile phase must be higher than 9.8, and alkaline media can lead to the degradation of labile compounds; the use of silica beads also limits its use. In this study, thermally responsive boronate affinity chromatographic material, namely poly(N‐isopropylacrylamide‐co‐N‐acryloyl‐3‐aminophenylboronic acid) grafted silica, was successfully prepared by atom transfer radical polymerization. Its structure was confirmed by IR spectroscopy and the graft ratio was 20.8%, determined by thermogravimetric analysis. Furthermore, the capture/release of adenosine, a cis‐diol, was performed from pH 5.0–9.0 and 10–50°C. The elution of adenosine was remarkably retarded at decreased temperatures and adenosine could be captured completely at 10°C at pH values of 5.0–9.0. The enrichment of adenosine could be achieved by simply changing the temperature from 10 to 50°C. Therefore, this material not only improved the stability of the silica, but was also suitable for the capture of oxidation‐sensitive biological analytes. Moreover, it could be used for the enrichment of cis‐diol‐containing compounds in LC with MS.     

Synthesis and application of boronic acid‐functionalized magnetic adsorbent for sensitive analysis of salbutamol residues in pig tissues

Salbutamol (SAL) is the most widely used β₂‐agonist drug for asthma and chronic obstructive pulmonary patients, but it is also often abused as feed additive. In recent years, the abuse of SAL has led to a large number of food safety incidents. Therefore, the monitoring of SAL residues in animal products is very important. A highly selective boronate affinity magnetic adsorbent was synthesized and developed for detection of trace levels of SAL residues in pig tissue samples. The obtained Fe₃O₄@SiO₂@FPBA(4‐formylphenylboronic acid) magnetic adsorbent showed good adsorption ability to catechol and SAL, and then it was successfully applied as special magnetic solid‐phase phase extraction adsorbent coupled with high‐performance liquid chromatography (HPLC) for simultaneous isolation and determination of cis‐diol compounds. The binding capacity of catechol and SAL reached 96 and 50 µmol/g, respectively. The method was successfully established for the detection of trace levels of SAL in pig tissue samples. The linear range extended from 0.32 to 800 µg/kg (R² = 0.9994). The limit of detection of SAL was 0.19 µg/kg. The recoveries were satisfactory (89.5–108.0%) at three spiked levels with RSD between 2.1 and 11.3%. These results indicated that the method has potential for enrichment and detection of trace levels of SAL residual in animal food products. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and evaluation of a molecularly imprinted sol–gel material as the solid‐phase extraction adsorbents for the specific recognition of cloxacilloic acid in cloxacillin

Highly selective molecularly imprinted polymers on the surface of silica gels were prepared by a sol–gel process and used as solid‐phase extraction adsorbents for the specific recognition, enrichment and detection of cloxacilloic acid in cloxacillin. The obtained polymers were characterized by scanning electron microscopy, FTIR spectroscopy, nitrogen adsorption and desorption, elemental analysis and thermogravimetric analysis. The imprinted polymers not only possessed high adsorption capacity (6.5 μg/mg), but also exhibited fast adsorption kinetics (they adsorb 80% of the maximum amount within 20 min) and excellent selectivity (the imprinted factor was 3.6). A method using the imprinted polymers as solid‐phase extraction adsorbents coupled with high‐performance liquid chromatography was established with good specificity, linearity (r = 0.9962), precision (ranging from 0.5 to 6.7%), accuracy (ranging from 93.9 to 97.7%) and extraction recoveries (ranging from 78.8 to 89.8%). The limits of detection and quantification were 0.07 and 0.25 mg/g, respectively. This work could provide a promising method in the enrichment, extraction and detection of allergenic impurities in the manufacture, storage and application of cloxacillin.     

Facile preparation of boronic acid‐functionalized magnetic nanoparticles with a high capacity and their use in the enrichment of cis‐diol‐containing compounds from plasma

The use of bronate affinity adsorbents is a new separation method that appeared recently with great potential for specific extraction of cis‐diol‐containing compounds. In this work,a new strategy for the facile construction of boronic acid‐functionalized Fe₃O₄ magnetic nanoparticles (Fe₃O₄@FPBA MNPs) with a high capacity was described. The extraction capacity of the Fe₃O₄@FPBA MNPs was determined to be 66.0 ± 2.7 µmol/g for catechol and 80.6 ± 2.0 µmol/g for dopamine, being higher than that for the reported methods. The Fe₃O₄@FPBA MNPs were used to extract four cis‐diol drugs: caffeic acid isopropyl ester, caffic acid bornyl ester, isopropyl 3‐(3,4‐dihydroxyphenyl)‐2‐hydroxypropanoate and 3‐(3, 4‐dihydroxyphenyl)‐2‐hydroxylpropionic acid – from the spiked rabbit plasma, and the recoveries of four drugs were between 87.29 and104.37% with relative standard deviations ranging from 1.34 to 8.81%. Under the most favorable conditions, the solid‐phase extraction combined with HPLC‐UV for the analysis of four drugs in plasma could eliminate interferences from endogenous components of the biological fluids and exhibited sufficient precision and accuracy. These results showed that the prepared Fe₃O₄@FPBA MNPs were qualified for efficiently enriching and determining the trace cis‐diol substances from biological samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Microfluidic chip with thermoresponsive boronate affinity for the capture–release of cis‐diol biomolecules

The polydimethylsiloxane microfluidic chip grafted with poly(N‐isopropylacrylamide‐3‐acrylamidephenylboronic acid) (P(NIPAAm‐co‐AAPBA)) was fabricated by UV‐induced grafting polymerization for the capture–release of cis‐diol‐containing biomolecules by temperature‐modulated changes instead of changing the pH value of the mobile phase. Based on the optimal time for benzophenone soaking and UV irradiation of grafting polymerization, P(NIPAAm‐co‐AAPBA) was successfully grafted on the polydimethylsiloxane substrates, which were characterized by scanning electron microscopy, water contact angle measurements, and Fourier transform infrared spectroscopy. The P(NIPAAm‐co‐AAPBA)‐grafted polydimethylsiloxane microfluidic chip can be successfully used for the capture and release of cis‐diol‐containing adenosine by adjusting the temperature from 4 to 55°C, and the result was validated by Triple Quad liquid chromatography with mass spectrometry. With further development, the fabricated polydimethylsiloxane microfluidic chips might be chosen as a potential tool for the capture and release of cis‐diol‐containing macromolecules, such as horseradish peroxidase and glycoprotein.     

Molecularly imprinted polymeric shell coated monodisperse‐porous silica microspheres as a stationary phase for microfluidic boronate affinity chromatography

Molecular imprinting of cis‐diol functionalized agents via boronate affinity interaction has been usually performed using nanoparticles as a support which cannot be utilized as a stationary phase in continuous microcolumn applications. In this study, monodisperse‐porous, spherical silica particles in the micron‐size range, with bimodal pore diameter distribution were selected as a new support for the synthesis of a molecularly imprinted boronate affinity sorbent, using a cis‐diol functionalized agent as the template. A specific surface area of 158 m²/g was achieved with the imprinted sorbent by using monodisperse‐porous silica microspheres containing both mesoporous and macroporous compartments as the support. High porosity originating from the macroporous compartment and sufficiently high particle size provided good column permeability to the imprinted sorbent in microcolumn applications. The mesoporous compartment provided a large surface area for the parking of imprinted molecules while the macroporous compartment facilitated the intraparticular diffusion of imprinted target within the microsphere interior. A microfluidic boronate affinity system was first constructed by using molecularly imprinted polymeric shell coated monodisperse‐porous silica microspheres as a stationary phase. The synthetic route for the imprinting process, the reversible adsorption/ desorption behavior of selected target and the selectivity of imprinted sorbent in both batch and microfluidic boronate affinity chromatography systems are reported.     

Selective Solid‐phase Extraction of Cu2+ by a Novel Cu(II)‐imprinted Silica Gel

A new Cu(II)‐imprinted salen functionalized silica gel adsorbent was synthesized by surface imprinting technique and was employed as a selective solid phase extraction material for Cu²⁺ removal from aqueous solutions. The samples were characterized by FT‐IR, ¹HNMR, ¹³CNMR, CHNS and DTG techniques. The BET surface area of the silica gel was also determined. The adsorbent was then used for removal of Cu²⁺ from aqueous solutions under different experimental conditions. It was concluded that the synthesized imprinted silica gel had higher selectivity and capacity compared to the non‐imprinted silica gel and the maximal adsorption capacity of 67.3 and 56.5 mg.g^?1 was obtained respectively for ion‐imprinted and non‐imprinted adsorbents. The relative selectivity factor (β) of 50.32 and 31.94 was obtained respectively for Cu²⁺/Ni²⁺ and Cu²⁺/Zn²⁺ pairs. The dynamic adsorption capacity of the imprinted adsorbent was close to the static adsorption capacity due to the fast kinetic of adsorption. Furthermore, the ion‐imprinted adsorbent was recovered and repeatedly used and satisfactory adsorption capacity with acceptable precision was obtained. Each experiment was repeated at least for three times and the mean and the standard deviation for each measurement were calculated. The applicability of the method was examined for Zayandehrood water as real sample. Acceptabe standard deviation was obtained.     

Functional Monolithic Materials for Boronate‐Affinity Chromatography via Schrock Catalyst‐Triggered Ring‐Opening Metathesis Polymerization

Monolithic polymeric materials are prepared via ring‐opening metathesis copolymerization of norborn‐2‐ene with 1,4,4a,5,8,8a‐hexahydro‐1,4,5,8‐exo,endo‐dimethanonaphthalene in the presence of macro‐ and microporogens, that is, of n‐hexane and 1,2‐dichloroethane, using the Schrock catalyst Mo(N‐2,6‐(2‐Pr)₂‐C₆H₃)(CHCMe₂Ph)(OCMe₃)₂. Functionalization of the monolithic materials is accomplished by either terminating the living metal alkylidenes with various functional aldehydes or by post‐synthesis grafting with norborn‐5‐en‐2‐ylmethyl‐4‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)benzoate. Finally, boronate‐grafted monolithic columns (100 × 3 mm i.d.) are successfully applied to the affinity chromatographic separation of cis‐diol‐based biomolecules.     

Ultrafast and Highly Selective Uranium Extraction from Seawater by Hydrogel‐like Spidroin‐based Protein Fiber

For the practical extraction of uranium from seawater, adsorbents with high adsorption capacity, fast equilibrium rate, high selectivity, and long service life are needed. Herein, a chimeric spidroin‐based super uranyl‐binding protein (SSUP) fiber was designed by fusing the gene of super uranyl‐binding protein (SUP) with the gene of spidroin. SUP endowed the SSUP fiber with high affinity and selectivity to uranium, and spidroin gave the SSUP fiber with high mechanical strength and high reusability. The wet SSUP fiber is a water‐rich hydrogel‐like structure, which provided abundant hydrophilic intermolecular space for the entrance of uranyl ions, and could accelerate the rate for uranium adsorption. In seawater, the SSUP fiber achieved a breakthrough uranium extraction capacity of 12.33 mg g^?1 with an ultrashort equilibration time of 3.5 days, suggesting that SSUP fiber might be a promising adsorbent for uranium extraction from the natural seawater.     

Synthesis of boronate‐functionalized organic‐inorganic hybrid monolithic column for the separation of cis‐diol containing compounds at low pH

In this work, an organic‐inorganic hybrid boronate affinity monolithic column was prepared via “one‐pot” process using 4‐vinylphenylboronic acid as organic monomer and divinylbenzene as cross‐linker. The effects of reaction temperature, solvents and composition of organic monomers on the column properties (e.g. morphology, permeability, and mechanical stability) were investigated. A series of test compounds including small neutral molecules, aromatic amines, and cis‐diol compounds were used to evaluate the retention behaviors of the prepared hybrid monolithic column. The results demonstrated that the prepared hybrid monolith exhibited mixed‐interactions including hydrophilicity, cation exchange, and boronate affinity interaction. The run‐to‐run, day‐to‐day and batch‐to‐batch reproducibilities of the prepared hybrid monolith for thiourea's retention time were satisfactory with the relative standard deviations (RSDs) less than 0.09, 1.45 and 4.05% (n = 3), respectively, indicating the effectiveness and practicability of the proposed method.     

Determination of catecholamines in urine using aminophenylboronic acid functionalized magnetic nanoparticles extraction followed by high‐performance liquid chromatography and electrochemical detection

A new method was developed for the simultaneous determination of three catecholamines in urine using aminophenylboronic acid functionalized magnetic nanoparticles extraction followed by high‐performance liquid chromatography with electrochemical detection. Novel aminophenylboronic acid functionalized magnetic nanoparticles were prepared by multi‐step covalent modification, and characterized by transmission electron microscopy, Fourier‐transformed infrared spectroscopy, X‐ray diffraction, and vibrating sample magnetometry. With the help of the high affinity between the boronate and cis‐diol group, the particles were used for the highly selective separation and enrichment of three major catecholamines, norepinephrine, epinephrine, and dopamine. Effects of the pH of the feed solution, the extraction time, the composition of the buffer solution, the amount of the magnetic particles, the elution conditions, and the recycling of aminophenylboronic acid functionalized magnetic nanoparticles were explored. Under the optimized conditions, 13–17‐fold enrichment factors were obtained. The linear ranges were 0.01–2.0 μg/mL for the studied analytes. The limits of detection and quantification were in the range of 2.0–7.9 and 6.7–26.3 ng/mL, respectively. The relative recoveries were in the range of 92–108%, with intraday and interday relative standard deviations lower than 6.8%. This method was successfully applied to analysis of catecholamines in real urine.     

Molecularly imprinted polymer coating on metal‐organic frameworks for solid‐phase extraction of fluoroquinolones from water

In this work, a novel surface molecularly imprinted polymer with high adsorption capacity, high adsorption rate, and high selectivity for fluoroquinolones was prepared on the surface of UiO‐66‐NH₂, which is a kind of metal‐organic framework. The surface morphology and adsorption properties of this molecularly imprinted polymer were investigated. The maximum adsorption capacity was 99.19 mg/g, and adsorption equilibrium was achieved within 65 s. Combined with reversed‐phase high‐performance liquid chromatography, the molecularly imprinted polymer was used to selectively enrich, separate and analyze fluoroquinolones present in lake water. The results showed that the recoveries of the four fluoroquinolones were 92.6–100.5%, and the relative standard deviations were 2.9–6.4% (n = 3). The novel molecularly imprinted polymer is an excellent adsorbent and has broad application prospects in the enrichment and separation of trace analytes in complex samples.     

Boronate Affinity Monolith with a Gold Nanoparticle‐Modified Hydrophilic Polymer as a Matrix for the Highly Specific Capture of Glycoproteins

As low abundance is the great obstacle for glycoprotein analysis, the development of materials with high efficiency and selectivity for glycoprotein enrichment is a prerequisite in glycoproteome research. Herein, we report a new kind of hydrophilic boronate affinity monolith by attaching 4‐mercaptophenylboronic acid (MPBA) with 2‐mercaptoethylamine (MPA) on the gold nanoparticle‐modified poly(glycidyl methacrylate‐co‐poly(ethylene glycol) diacrylate)) monolith for glycoprotein enrichment. With poly(ethylene glycol) diacrylate as the cross‐linker and the further modification of gold nanoparticles, the matrix has advantages of good hydrophilicity and enhanced surface area, which are beneficial to improve the enrichment selectivity and efficiency for glycoproteins. The attachment of MPBA and MPA provide intramolecular B?N coordination, which could further enhance the specificity of glycoprotein capture. Such a boronate affinity monolith was applied to enrich horseradish peroxidase (HRP) from the mixture of HRP and bovine serum albumin (BSA), and high selectivity was obtained even at a mass ratio of 1:1000. In addition, the binding capacity of ovalbumin on such monolith reached 390 μg g^?1. Furthermore, the average recovery of HRP on the prepared affinity monoliths was (84.8±1.9) %, obtained in three times enrichment with the same column. Finally, the boronate affinity monolith was successfully applied for the human‐plasma glycoproteome analysis. As a result, 160 glycoproteins were credibly identified from 9 μg of human plasma, demonstrating the great potential of such a monolith for large‐scale glycoproteome research.     

Extraction and identification of matrine‐type alkaloids from Sophora moorcroftiana using double‐templated molecularly imprinted polymers with HPLC–MS/MS

Double‐templated molecularly imprinted polymers with specific recognition of three matrine‐type alkaloids were prepared using matrine and oxymatrine as the template molecules. An approach based on double‐templated molecularly imprinted solid‐phase extraction coupled with high‐performance liquid chromatography and tandem mass spectrometry was then developed to extract and purify matrine, oxymatrine, and sophocarpine from Sophora moorcroftiana in the Tibetan plateau herbs. The polymers were characterized by Fourier‐transform infrared spectroscopy and scanning electron microscopy. Their adsorption characteristics were evaluated using adsorption kinetics, isotherms, selectivity, and recycling experiments. This polymer exhibited excellent molecular recognition ability and good selectivity. The obtained polymers as adsorbent was further used for the determination of three matrine‐type alkaloids coupled to high‐performance liquid chromatography with tandem mass spectrometry, the recoveries of three matrines spiked at three concentration levels in samples were 73.25–98.42% (n = 5) with a relative standard deviation less than 6.82%. The limits of detection for the method were 9.23–15.42 μg/kg (S/N = 3). This proposed method was assessed to be an effective method for simultaneous extraction, isolation, and identification of matrine, oxymatrine, and sophocarpine from Sophora moorcroftiana.     

Quick and selective extraction of Z‐ligustilide from Angelica sinensis using magnetic multiwalled carbon nanotubes

A facile and highly efficient magnetic solid‐phase extraction method has been developed for Z‐ligustilide, the major therapeutic agent in Angelica sinensis. The solid‐phase adsorbent material used was prepared by conjugating carbon nanotubes with magnetic Fe₃O₄ nanoparticles via a hydrothermal reaction. The magnetic material showed a high affinity toward Z‐ligustilide due to the π–π stacking interaction between the carbon nanotubes and Z‐ligustilide, allowing a quick and selective exaction of Z‐ligustilide from complex sample matrices. Factors influencing the magnetic solid‐phase extraction such as the amount of the added adsorbent, adsorption and desorption time, and desorption solvent, were investigated. Due to its high extraction efficiency, this method was proved highly useful for sample cleanup/enrichment in quantitative high‐performance liquid chromatography analysis. The proposed method had a linear calibration curve (R² = 0.9983) over the concentration between 4 ng/mL and 200 μg/mL Z‐ligustilide. The accuracy of the method was determined by the recovery, which was from 92.07 to 104.02%, with the relative standard deviations >4.51%.     

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.