Molecularly imprinted polymer functionalized magnetic Fe3O4 for the highly selective extraction of triclosan

We present a facile strategy to prepare the molecularly imprinted polymers layer on the surface of Fe₃O₄ nanoparticles with core‐shell structure via sol–gel condensation for recognition and enrichment of triclosan. The Fe₃O₄ nanoparticles were first synthesized by a solvothermal method. Then, template triclosan was self‐assembled with the functional monomer 3‐aminopropyltriethoxysilane on the silica‐coated Fe₃O₄ nanoparticles in the presence of ethanol and water. Finally, the molecularly imprinted polymers were formed on the surface of silica‐coated Fe₃O₄ nanoparticles to obtain the product. The morphology, magnetic susceptibility, adsorption, and recognition property of magnetic molecularly imprinted polymers were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffractometry, vibrating sample magnetometry, and re‐binding experiments. The magnetic molecularly imprinted polymers showed binding sites with good accessibility, fast adsorption rate, and high adsorption capacity (218.34 μg/g) to triclosan. The selectivity of magnetic molecularly imprinted polymers was evaluated by the rebinding capability of triclosan and two other structural analogues (phenol and p‐chlorophenol) in a mixed solution and good selectivity with an imprinting factor of 2.46 was obtained. The application of triclosan removal in environmental samples was demonstrated.     

Preparation of magnetic glycoprotein‐imprinted nanoparticles with dendritic polyethyleneimine as a monomer for the specific recognition of ovalbumin from egg white

Glycoproteins are crucial in massive physiological events and clinical application. It is necessary to prepare new materials to isolate the specific glycoprotein. New and simple core–shell molecularly imprinted polymers were prepared by surface imprinting. The polymers are synthesized with magnetic nanoparticles as the core, water‐soluble dendritic polyethyleneimine as the monomer and the ovalbumin as the template. The prepared imprinted polymers showed thin imprinted shell, biocompatibility and superparamagnetic properties. The resultant materials exhibited fast kinetics, high adsorption capacity, perfect selectivity and reusability. More important, they can absorb the template glycoprotein from the neutral solution and successfully be applied to recognize the ovalbumin from egg white, which means that they can provide an alternate method to isolate glycoprotein from bodily fluids.     

Preparation of novel bovine hemoglobin surface-imprinted polystyrene nanoparticles with magnetic susceptibility

In this research, a surface imprinting strategy has been adopted in protein imprinting. Bovine hemoglobin surface-imprinted polystyrene (PS) nanoparticles with magnetic susceptibility have been synthesized through multistage core-shell polymerization system using 3-aminophenylboronic acid (APBA) as functional and cross-linking monomers. Superparamagnetic molecularly imprinted polystyrene nanospheres with poly(APBA) thin films have been synthesized and used for the first time for protein molecular imprinting in an aqueous solution. The magnetic susceptibility is imparted through the successful encapsulation of Fe₃O₄ nanoparticles. The morphology, adsorption, and recognition properties of superparamagnetic molecularly imprinted polymers (MIPs) have been investigated using transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, and vibrating sample magnetometer. Rebinding experimental results show that poly(APBA) MIPs-coated superparamagnetic PS nanoparticles have high adsorption capacity for template protein bovine hemoglobin and comparatively low nonspecific adsorption. The imprinted superparamagnetic nanoparticles could easily reach the adsorption equilibrium and achieve magnetic separation in an external magnetic field, thus avoiding some problems of the bulk polymer.     

Synthesis and characterization of photo‐responsive magnetic molecularly imprinted microspheres for the detection of sulfonamides in aqueous solution

A dual responsive molecularly imprinted polymer sensitive to both photonic and magnetic stimuli was successfully prepared for the detection of four sulfonamides in aqueous media. The photoresponsive magnetic molecularly imprinted polymer was prepared by surface imprinting polymerization using superparamagnetic Fe₃O₄ nanoparticles functionalized with a silica layer as a support, water‐soluble 4‐[(4‐methacryloyloxy)phenylazo]benzenesulfonic acid as the functional monomer, and sulfadiazine as the template. The magnetic molecularly imprinted polymers showed specific affinity to sulfadiazine and its structural analogs in aqueous media. Upon alternate irradiation at 365 and 440 nm, the quantitative bind and release of the four sulfonamides by magnetic molecularly imprinted polymers occurred. Furthermore, the prepared magnetic molecularly imprinted polymers were used as solid‐phase extraction material selectively extracted the four sulfonamides from water samples with good recoveries. Thus, a simple, convenient, and reliable detection method for sulfonamides in the environment based on responsive magnetic molecularly imprinted polymers was successfully established.     

Selective separation and enrichment of glibenclamide in health foods using surface molecularly imprinted polymers prepared via dendritic grafting of magnetic nanoparticles

In this paper, the novel surface molecularly imprinted polymers based on dendritic‐grafting magnetic nanoparticles were developed to enrich and separate glibenclamide in health foods. The density functional theory method was used to give theoretical directions to the synthesis of molecularly imprinted polymers. The polymers were prepared by using magnetic nanoparticles as supporting materials, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross‐linker. The characteristics of magnetic nanoparticles and polymers were measured by transmission electron microscope and SEM, respectively. The enriching ability of molecularly imprinted polymers was measured by Freundlich Isotherm. The molecularly imprinted polymers were used as dispersive SPE materials to enrich, separate, and detect glibenclamide in health foods by HPLC. The average recoveries of glibenclamide in spiked health foods were 81.46–93.53% with the RSD < 4.07%.     

Efficient synthesis of molecularly imprinted polymers with bio‐recognition sites for the selective separation of bovine hemoglobin

We developed a facile approach to the construction of bio‐recognition sites in silica nanoparticles for efficient separation of bovine hemoglobin based on amino‐functionalized silica nanoparticles grafting by 3‐aminopropyltriethoxylsilane providing hydrogen bonds with bovine hemoglobin through surface molecularly imprinting technology. The resulting amino‐functionalized silica surface molecularly imprinted polymers were characterized using scanning electron microscope, transmission electronic microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. Results showed that the as‐synthesized imprinted polymers exhibited spherical morphology and favorable thermal stability. The binding adsorption experiments showed that the imprinted polymers can reach equilibrium within 1 h. The Langmuir isotherm and pseudo‐second‐order kinetic model fitted the adsorption data well. Meanwhile, the imprinted polymers possessed a maximum binding capacity up to 90.3 mg/g and highly selectivity for the recognition of bovine hemoglobin. Moreover, such high binding capacity and selectivity retained after eight cycles, indicating the good stability and reusability of the imprinted polymers. Finally, successful application in the selective recognition of bovine hemoglobin from a real bovine blood sample indicated that the imprinted polymers displayed great potentials in efficient purification and separation of target proteins.     

Preparation of magnetic molecularly imprinted polymers by atom transfer radical polymerization for the rapid extraction of avermectin from fish samples

A novel and highly efficient approach to obtain magnetic molecularly imprinted polymers is described to detect avermectin in fish samples. The magnetic molecularly imprinted polymers were synthesized by surface imprinting polymerization using magnetic multiwalled carbon nanotubes as the support materials, atom transfer radical polymerization as the polymerization method, avermectin as template, acrylamide as functional monomer, and ethylene glycol dimethacrylate as crosslinker. The characteristics of the magnetic molecularly imprinted polymers were assessed by using transmission electron microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, vibrating sample magnetometry, X‐ray diffraction, and thermogravimetric analysis. The binding characteristics of magnetic molecularly imprinted polymers were researched through isothermal adsorption experiment, kinetics adsorption experiment, and the selectivity experiment. Coupled with ultra high performance liquid chromatography and tandem mass spectrometry, the extraction conditions of the magnetic molecularly imprinted polymers as adsorbents for avermectin were investigated in detail. The recovery of avermectin was 84.2–97.0%, and the limit of detection was 0.075 μg/kg. Relative standard deviations of intra‐ and inter‐day precisions were in the range of 1.7–2.9% and 3.4–5.6%, respectively. The results demonstrated that the extraction method not only has high selectivity and accuracy, but also is convenient for the determination of avermectin in fish samples.     

Protein Denaturation Through the Use of Magnetic Molecularly Imprinted Polymer Nanoparticles

The inhibition of the protein function for therapeutic applications remains challenging despite progress these past years. While the targeting application of molecularly imprinted polymer are in their infancy, no use was ever made of their magnetic hyperthermia properties to damage proteins when they are coupled to magnetic nanoparticles. Therefore, we have developed a facile and effective method to synthesize magnetic molecularly imprinted polymer nanoparticles using the green fluorescent protein (GFP) as the template, a bulk imprinting of proteins combined with a grafting approach onto maghemite nanoparticles. The hybrid material exhibits very high adsorption capacities and very strong affinity constants towards GFP. We show that the heat generated locally upon alternative magnetic field is responsible of the decrease of fluorescence intensity.     

Poly(amino acid)-based thermoresponsive molecularly imprinted magnetic nanoparticles for specific recognition and release of lysozyme

In this study, poly(amino acid)-based thermoresponsive molecularly imprinted magnetic nanoparticles for recognition and release of lysozyme was prepared via surface imprinting method. For constructing the molecularly imprinted polymer (MIP) layer, amino acid-based thermoresponsive monomer (N-methacryloyl-l-alanine methyl ester, MA-L-Ala-OMe) was mainly selected for the functional monomer along with N,N′-methylenebis(acrylamide) as the crosslinker. The resultant magnetic MIP nanoparticles were characterized in detail. Meanwhile, the dynamic light scattering studies and swelling ratios measurements were carried out for demonstrating the thermoresponsive property of the imprinted nanoparticles. The prepared magnetic MIP nanoparticles showed good adsorption capacity and selective recognition properties to lysozyme. Moreover, the fast adsorption process could reach equilibrium within 15 min. Importantly, the capture and release of lysozyme could be easily realized simply by altering the temperature of aqueous solution. Furthermore, the prepared imprinted nanoparticles were applied to separate lysozyme from the real egg white samples. The results proved that the thermoresponsive MIPs based on MA-L-Ala-OMe have great potential for selectively enriching target proteins in real samples.     

Facile and versatile strategy to prepare magnetic molecularly imprinted particles based on the coassembly of magnetic nanoparticles and amphiphilic random copolymers

Magnetic molecularly imprinted polymer nanoparticles for bisphenol A were prepared by coassembling magnetic nanoparticles and amphiphilic random copolymers. Under optimized conditions, bisphenol A as template molecules, magnetic molecularly imprinted polymer particles with regular morphology, small size, good monodispersity, and high content of OA‐Fe₃O₄ were prepared by the coassembly method using P(MMA‐co‐MAA) with monomer ratio of 9:1. These magnetic molecularly imprinted polymer particles could be rapidly collected by an external magnet within 1 min. The saturated adsorption capacity of the magnetic molecularly imprinted polymer for bisphenol A was 201.5 mg/g, and the imprinting factor was 2.5. The separation factors for bisphenol A to β‐estradiol, estriol, and diethylstilbestrol was 3.1, 2.9, and 3.7, respectively. Unlike assembling amphiphilic copolymer in the selective solvent, the coassembly process was simple and rapid. Therefore, the present work provided a facile and versatile approach to construct magnetic molecularly imprinted polymer nanoparticles under mild conditions.     

Molecularly imprinted magnetic nanoparticles for the micro solid‐phase extraction of thiabendazole from citrus samples

The preparation of molecularly imprinted core–shell magnetic nanoparticles and their subsequent use in the solid‐phase extraction of thiabendazole from citrus sample extracts is described. Molecularly imprinted core–shell magnetic nanoparticles were prepared by the precipitation copolymerization of the imprinting polymerization mixture on the surface of vinyl‐modified silica magnetic nanoparticles and were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The obtained molecularly imprinted core–shell magnetic nanoparticles exhibited a high selectivity for thiabendazole and were easily collected and separated by an external magnetic field without additional centrifugation or filtration steps. Under optimum conditions, a magnetic molecularly imprinted solid‐phase extraction method was developed allowing the extraction of thiabendazole from citrus sample extracts and final determination by high‐performance liquid chromatography with fluorescence detection. The detection limit was 0.2 mg/kg, far lower than the maximum residue limit established within the European Union for thiabendazole in citrus samples.     

Magnetic molecularly imprinted polymers synthesized by surface‐initiated reversible addition‐fragmentation chain transfer polymerization for the enrichment and determination of synthetic estrogens in aqueous solution

Magnetic molecularly imprinted polymers have attracted significant interest because of their multifunctionality of selective recognition of target molecules and rapid magnetic response. In this contribution, magnetic molecularly imprinted polymers were synthesized via surface‐initiated reversible addition addition‐fragmentation chain transfer polymerization using diethylstilbestrol as the template for the enrichment of synthetic estrogens. The uniform imprinted surface layer and the magnetic property of the magnetic molecularly imprinted polymers favored a fast binding kinetics and rapid analysis of target molecules. The static and selective binding experiments demonstrated a desirable adsorption capacity and good selectivity of the magnetic molecularly imprinted polymers in comparison to magnetic non‐molecularly imprinted polymers. Accordingly, a corresponding analytical method was developed in which magnetic molecularly imprinted polymers were employed as magnetic solid‐phase extraction materials for the concentration and determination of four synthetic estrogens (diethylstilbestrol, hexestrol, dienestrol, and bisphenol A) in fish pond water. The recoveries of these synthetic estrogens in spiked fish pond water samples ranged from 61.2 to 99.1% with a relative standard deviation of lower than 6.3%. This study provides a versatile approach to prepare well‐defined magnetic molecularly imprinted polymers sorbents for the analysis of synthetic estrogens in water solution.     

Interfacial Molecular Imprinting in Nanoparticle-Stabilized Emulsions

A new interfacial nano and molecular imprinting approach is developed to prepare spherical molecularly imprinted polymers with well-controlled hierarchical structures. This method is based on Pickering emulsion polymerization using template-modified colloidal particles. The interfacial imprinting is carried out in particle-stabilized oil-in-water emulsions, where the molecular template is presented on the surface of silica nanoparticles during the polymerization of the monomer phase. After polymerization, the template-modified silica nanoparticles are removed from the new spherical particles to leave tiny indentations decorated with molecularly imprinted sites. The imprinted microspheres prepared using the new interfacial nano and molecular imprinting have very interesting features: a well-controlled hierarchical structure composed of large pores decorated with easily accessible molecular binding sites, group selectivity toward a series of chemicals having a common structural moiety (epitopes), and a hydrophilic surface that enables the MIPs to be used under aqueous conditions.     

Preparation and evaluation of temperature and magnetic dual‐responsive molecularly imprinted polymers for the specific enrichment of formononetin

Thermo‐responsive magnetic molecularly imprinted polymers were prepared by simple surface molecular imprinting polymerization for the selective adsorption and enrichment of formononetin from Trifolium pretense by temperature regulation. Using formononetin as a template, N‐isopropylacrylamide as the thermo‐responsive functional monomer, and methacrylic acid as an assisting functional monomer, the polymers were synthesized on the surface of the magnetic substrate. The results show that imprinted polymers attained controlled adsorption of formononetin in response to the temperature change, with large adsorption capacity (16.43 mg/g), fast kinetics (60 min) and good selectivity at 35°C compared with that at 25 and 45°C. The selectivity experiment indicated that the materials had excellent recognition ability for formononetin and the selectivity factors were between 1.32 and 2.98 towards genistein and daidzein. The excellent linearity was attained in the range of 5–100 μg/mL, with low detection limits and low quantitation limits of 0.017 and 0.063 μg/mL, respectively. Furthermore, the thermo‐responsive magnetic molecularly imprinted polymers were successfully utilized for enriching and purifying formononetin from Trifolium pretense. The analytical results indicate that the imprinted polymers are promising materials for selective identification and enrichment of formononetin in complicated herbal medicines by simple temperature‐responsive regulation.     

Synthesis of core‐shell magnetic molecularly imprinted polymer for the selective determination of imidacloprid in apple samples

This work demonstrates the synthesis and characterization of core‐shell magnetic molecularly imprinted polymers based on surface imprinting using methacryloyl chloride as a functional monomer for the selective extraction of imidacloprid (template) from apple fruit. The characterization analysis results ensured the successful synthesis of the magnetic molecularly imprinted polymers owing to their heterogeneous structure and good magnetic properties. An isothermal binding test was assessed with a pseudo‐second‐order kinetic model, and the kinetic results fit well to the Freundlich isothermal model. The polymers exhibited an adsorption capacity of 5.75 mg/g for the target analyte with a good selective extraction ability. In addition, the polymers can be reused several times without significant performance loss. The molecularly imprinted polymers showed good performance in the analysis of spiked apple sample with a linear range of 0.05–1.0 mg/L, a limit of detection of 0.048 mg/L and a limit of quantification of 0.146 mg/L (S/N = 3/10). The recoveries of the samples were 77.66–96.57% and their respective relative standard deviations were 3.36–0.45%. All the results indicated that the proposed method provided good selective extraction, as qualifying the analytical standards.     

Selective enrichment and separation of phosphotyrosine peptides by thermosensitive molecularly imprinted polymers

Novel thermosensitive molecularly imprinted polymers were successfully prepared using the epitope imprinting approach in the presence of the mimic template phenylphosphonic acid, the functional monomer vinylphosphonic acid‐Ti⁴⁺, the temperature‐sensitive monomer N‐isopropylacrylamide and the crosslinker N,N′‐methylenebisacrylamide. The ratio of the template/thermosensitive monomers/crosslinker was optimized, and when the ratio was 2:2:1, the prepared thermosensitive molecularly imprinted polymers had the highest imprinting factor. The synthetic thermosensitive molecularly imprinted polymers were characterized by Fourier transform infrared spectroscopy to reveal the combination and elution processes of the template. Then, the adsorption capacity and thermosensitivity was measured. When the temperature was 28°C, the imprinting factor was the highest. The selectivity and adsorption capacity of the thermosensitive molecularly imprinted polymers for phosphotyrosine peptides from a mixture of three tailor‐made peptides were measured by high‐performance liquid chromatography. The results showed that the thermosensitive molecularly imprinted polymers have good selectivity for phosphotyrosine peptides. Finally, the imprinted hydrogels were applied to specifically adsorb phosphotyrosine peptides from a sample mixture containing phosphotyrosine and a tryptic digest of β‐casein, which demonstrated high selectivity. After four rebinding cycles, 78.9% adsorption efficiency was still retained.     

Magnetic deep eutectic solvents molecularly imprinted polymers for the selective recognition and separation of protein

A novel and facile magnetic deep eutectic solvents (DES) molecularly imprinted polymers (MIPs) for the selective recognition and separation of Bovine hemoglobin (BHb) was prepared. The new-type DES was adopted as the functional monomer which would bring molecular imprinted technology to a new direction. The amounts of DES were optimized. The obtained magnetic DES-MIPs were characterized with fourier transform infrared spectrometry (FT-IR), thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), dynamic light scattering (DLS), elemental analysis and vibrating sample magnetometer (VSM). The results suggested that the imprinted polymers were successfully formed and possessed a charming magnetism. The maximum adsorption capability (Q_max) and dissociation constant (K_L) were analyzed by Langmuir isotherms (R² = 0.9983) and the value were estimated to be 175.44 mg/g and 0.035 mg/mL for the imprinted particles. And the imprinted particles showed a high imprinting factor of 4.77. In addition, the magnetic DES-MIPs presented outstanding recognition specificity and selectivity so that it can be utilized to separate template protein from the mixture of proteins and real samples. Last but not least, the combination of deep eutectic solvents and molecular imprinted technology in this paper provides a new perspective for the recognition and separation of proteins.     

Photoregulated uptake and release of drug by an organic–inorganic hybrid sol–gel material

A photo-responsive molecularly imprinted sol–gel organic-inorganic hybrid material prepared by covalent imprinting of the template-functional monomer complex formed between 4,4′-dihydroxylazobenzene and ibuprofen was developed to explore the photo-regulated uptake and release of drug by a silicate-based smart molecularly imprinted materials. After imprinting, the template molecules (ibuprofen) were removed via hydrolysis in acid, and accurate cavities were left, which could be used as the receptor recognition sites for ibuprofen. The new organic–inorganic hybrid material shows specific affinity to ibuprofen and reversible uptake and release of ibuprofen upon alternate irradiation at 365 and 440 nm, respectively. The favorable binding strength of the imprinted receptor sites in the molecularly imprinted polymer (MIP) for ibuprofen is found to be 2.28 × 10³ M⁻¹. Density of receptor sites in the MIP material was 4.0 μmol/g—MIP.     

分子印迹溶胶-凝胶材料的制备及应用

分子印迹技术是制备对特定分子具有选择性识别的聚合物的技术。分子印迹技术与溶胶-凝胶过程相结合,可设计多孔无机主体,增强分子识别能力,并具有极好的热稳定性和水解稳定性。改变溶胶-凝胶过程的条件,可制备具有最佳孔隙率和表面积,并用于分离复杂的混合物、选择性吸附富集模板分子(或目标分子)、催化、微合成器应用的分子印迹溶胶-凝胶材料。综述了溶胶．凝胶技术和分子印迹技术的特点,分子印迹溶胶-凝胶技术和分子印迹溶胶．凝胶材料的概念、基本原理、制备方法及应用。     

Magnetic molecularly imprinted polymers for recognition and enrichment of polysaccharides from seaweed

New magnetic molecularly imprinted polymers with two templates were fabricated for the recognition of polysaccharides (fucoidan and alginic acid) from seaweed by magnetic solid‐phase extraction, and the materials were modified by seven types of deep eutectic solvents. It was found that the deep eutectic solvents magnetic molecularly imprinted polymers showed stronger recognition and higher recoveries for fucoidan and alginic acid than magnetic molecularly imprinted polymers, and the deep eutectic solvents‐4‐magnetic molecularly imprinted polymers had the best effects. The practical recovery of the two polysaccharides (fucoidan and alginic acid) purified with deep eutectic solvents‐4‐magnetic molecular imprinted polymers in seaweed under the optimal conditions were 89.87, and 92.0%, respectively, and the actual amounts extracted were 20.6 and 18.7 μg/g, respectively. To sum up, the developed method proved to be a novel and promising method for the recognition of complex polysaccharide samples from seaweed.