Bio‐inspired synthesis of molecularly imprinted nanocomposite membrane for selective recognition and separation of artemisinin

Inspired from the highly bioadhesive performance of mussel protein, a simple, yet efficient synthetic method for efficiently imprinting of Artemisinin (Ars) was developed to prepare the bio‐inspired molecularly imprinted membranes (MIMs) via atom transfer radical polymerization (ATRP). In this work, attributed to the unique properties of polydopamine (pDA) modified layers and ATRP technology, the uniform recognition sites for efficiently selective extraction of the Ars with high stability could be obtained on the MIMs surfaces. In addition, the maximum adsorption capacity of the MIMs is 158.85 mg g^?1 by the Langmuir isotherm model, which is remarkable higher than NIMs. Additionally, because of the formation of the uniform specific recognition cavities on membrane surfaces, the as‐prepared MIMs exhibited a rapid adsorption dynamics and well‐fitted for the pseudo‐second‐order rate equation, also, possessed an excellent per‐selectivity performance (β_{artemether/Ars} values is 0.18) of template molecule, which clearly demonstrated the potential value of this method in the selective separation and purification of Ars. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43405.     

Graphene‐based molecularly imprinted polymer for separation and pre‐concentration of trace polycyclic aromatic hydrocarbons in environmental water samples

A composite of reduced graphene oxide and pyrene‐imprinted polymer was synthesized and employed as a solid phase for extraction of five selected polycyclic aromatic hydrocarbons (PAHs) from water samples. Gas chromatography‐time of flight/mass spectrometry was employed in the analysis of the extracts. The composite was prepared by a free radical polymerization of methacrylic acid and 4‐vinylpyridine as monomers and ethylene glycol dimethacrylate as a crosslinker. The adsorption studies were carried out through batch binding studies. The binding capacity for the imprinted and non‐imprinted composite was 101.83 and 68.21 µg g^?1, respectively. The adsorption followed the pseudo 2nd order and well fitted the Langmuir isotherm. Mean recoveries ranging from 73% to 105.4% for both spiked deionized water and environmental water samples were obtained when the imprinted composites were employed in solid phase extraction of the PAHs. The composites could be re‐used for five times without a significant loss in recoveries. The proposed method was employed for the analysis of spiked environmental water samples and did not show significant changes in the recoveries showing there were no matrix interferences. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45300.     

Solid-phase extraction materials based on molecularly imprinted polymers for recognition of pyrethroids

A novel recognition material for detection of kinds of pyrethroids was successfully synthesized by molecular imprinting technology. 3-Phenoxybenzoic acid (PBA) usually could be the antigen to prepare the polyclonal antibody. In this work, the recognition material was prepared utilizing PBA as the template, methacrylicacid as the functional monomer and ethylene glycol dimethacrylate as the crosslinker. The recognition material was characterized by atomic force microscope, adsorption equilibrium and selectivity experiments. The results showed that the recognition material has been successfully prepared and recognized four pyrethroids (fenpropathrin, deltamethrin, fenvalerate, and cyhalothrin). The recognition material was utilized as sorbents in solid-phase extraction for separation and detection of pyrethroids in practically samples. Under the optimal conditions, the recoveries were ranging from 74.3 to 111.0%. Therefore, novel materials for pyrethroids are very promising for future applications. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48919.     

Preparation and characterization of magnetic molecularly imprinted polymers for selective recognition of 3‐methylindole

In this work, magnetic molecularly imprinted polymers (MMIPs) were used as novel adsorbents for selective adsorption of 3‐methylindole from model oil. The MMIPs were synthesized by precipitation polymerization and surface molecularly imprinted technique, using Fe₃O₄ nanoparticles as magnetically susceptible component, methylacrylic acid as dressing agent and functional monomer, ethylene glycol dimethacrylate as crosslinker, and 3‐methylindole as template molecule. The MMIPs were characterized by Fourier‐transform infrared spectroscopy, scanning electron microscopy, vibrating sample magnetometer, and thermogravimetric analyzer, respectively. The adsorption performances of MMIPs were investigated by batch adsorption experiments in terms of kinetics, isotherms, and selective recognition adsorption, respectively. The results indicate that MMIPs have high recognition ability and fast binding kinetics for 3‐methylindole. Meanwhile, the adsorption equilibrium time was about 2 h and the equilibrium adsorption amount was ～38 mg g^?1 at 298 K. The heterogeneous MMIPs were modeled with pseudo‐second‐order and Langmuir isotherm equation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2859–2866, 2013     

Selective recognition of beta‐cypermethrin by molecularly imprinted polymers based on magnetite yeast composites

Magnetic nanoparticles were attached to yeast by co‐precipitation reaction of FeCl₃·6H₂O and FeCl₂·4H₂O. Then, based on magnetite yeast composites (M@Y), the magnetic molecularly imprinted polymers (MMIPs) were synthesized for the selective recognition of beta‐cypermethrin (PP₃₂₁). MMIPs were characterized by scanning electron microscopy, X‐ray diffraction, vibrating sample magnetometer, Fourier transform infrared analysis, thermogravimetric analysis, and elemental analysis. MMIPs exhibited uniform morphology and magnetic property (Ms = 17.87 emu/g) and thermal stability. Batch mode adsorption studies were carried out to investigate the specific adsorption equilibrium, kinetics, and selective recognition. The Langmuir isotherm model was fitted to the equilibrium data slightly better than the Freundlich model, and the adsorption capacity of MMIPs was 39.64 mg/g at 298 K. The kinetic properties of MMIPs were well described by the pseudo‐second‐order equation. Hydrogen bonds between methacrylic acid and PP₃₂₁ were mainly responsible for the adsorption mechanism. The MMIPs prepared were applied to the separation of PP₃₂₁ from experimental samples successfully. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Precipitation polymerization of molecularly imprinted polymers for recognition of melamine molecule

Molecular imprinted polymer microspheres (MIPs) were prepared by precipitation polymerization using melamine as template molecule, methacrylic acid (MAA) as functional monomer, trimethylol‐propane trimethacrylate (TRIM) as crosslinking agent, acetonitrile as solvent and dispersion medium. Release of the template was performed by continuous extraction with methanol containing 10% acetic acid. The microspheres were observed by scanning electron microscopy (SEM). The perfect microspheres were produced when the addition of crosslinker was 7.48 mmol. The binding capacity of MIPs was examined, Q_max = 68.36 μmol g^?1, and the dissociation constant at binding site of MIPs, K_d = 0.761, was estimated. Compared with the performance of conventional imprinted polymer, the imprinted microspheres showed high selectivity in special binding to template molecule. The imprinted microspheres could be used as the stationary phase in HPLC or SPE for selective extraction of melamine in daily products. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Clozapine recognition via molecularly imprinted polymers; bulk polymerization versus precipitation method

Two clozapine (CLZ) imprinted polymers were prepared by bulk and precipitation methods. Methacrylic acid and ethylene glycol dimethacrylate (EDMA) were used as functional and crosslinker monomers, respectively. The mean diameter and particle size distribution of the imprinted (P‐MIP) and nonimprinted (P‐NIP) particles obtained in precipitation method were examined. A conventional batch‐adsorption test was applied for characterization of CLZ–polymer interaction. Dissociation constant (K_D) and maximum binding sites (B_max) were calculated using Scatchard analysis. To evaluate the recognition properties of polymers, phenytoin (PTN) binding to each polymer was also studied and compared to CLZ. The imprinting factor (IF) and selectivity factor (α) were also determined for each polymer. Average diameter and polydispersity of P‐MIP were 925 nm and 0.17, respectively. The data for P‐NIP were 1.05 μm and 0.18. The K_D, IF, and α values calculated for P‐MIP were 0.45 μM, 3.26, and 17.43, respectively. The data for imprinted polymer, prepared by bulk polymerization (B‐MIP), were 14.5 μM, 1.95, and 3.67. These results demonstrated that precipitation polymerization is a more convenient, more effective, and more reproducible method than bulk polymerization for the synthesis of uniformly sized micron and submicron‐imprinted polymer particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Recent advances in molecularly imprinted polymers in food analysis

Food security as a world issue has received increasing concern, and therefore, effective analytical methods and technologies have been continuously developed. However, the matrix complexity of food samples and the trace/ultratrace presence of targeted analytes require highly efficient cleanup and enrichment materials and procedures. Molecularly imprinted polymers (MIPs) with specific recognition abilities as versatile materials are being increasingly developed for diverse species in various fields, especially in food analysis. In this review, we mainly summarize the recent advances in MIPs used for food matrices over the last 5 years. We focus on toxic and harmful substances, such as pesticide/drug residues, heavy metals, microbial toxins, and additives. Some relatively new preparation methods involving surface imprinting, composites, and stimuli responsiveness are reviewed. Different MIPs as solid‐phase adsorbents in solid‐phase extraction, solid‐phase microextraction, matrix solid‐phase dispersion, stirring bar sorptive extraction, and magnetic material extraction and as stationary phases in chromatographic separation for foodstuff have been comprehensively summarized. MIP‐based biomimetic sensing and enzymelike catalysis receive special attention. Moreover, some limitations and comparisons related to MIPs performances are also discussed. Finally, some significant attempts to further promote MIP properties and applications to ensure food safety are discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40766.     

Simple preparation and characterization of molecularly imprinted nylon 6 nanofibers for the extraction of bisphenol A from wastewater

Nylon 6 nanofibers incorporated with molecularly imprinted polymers (MIPs) were successfully fabricated by electrospinning with fiber diameters in the range 80–145 nm. Then, they were used as a new material for the extraction of selected bisphenol A (BPA) in water samples. Field emission scanning electron microscopy images revealed that the nanofibers had a smooth morphology with a good incorporation of MIPs. The Fourier transform infrared and energy-dispersive X-ray spectroscopy results also confirmed the formation of the MIPs in the nanofibers. Furthermore, Raman spectroscopy showed that the crystalline structure of the pristine nylon 6 nanofiber was a kind of α form, and the incorporation of MIPs led to a γ-form structure in the nanofibers; this proved the interactions between nylon 6 and the MIPs. Adsorption studies also confirmed that the adsorption efficiency of BPA onto the molecularly imprinted polymer nanofibers (MIP-NFs; 83.5%) was much greater than that onto nonimprinted polymer nanofibers (NIP-NFs; 36.8%). Also, the imprinting factor was 3.4; this strongly implied the successful formation of molecularly imprinted cavities on the MIP-NFs with a strong affinity to BPA. The maximum adsorption capacity of the MIP-NFs was 103.8 mg/g. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47112.     

Water‐compatible imprinted polymers based on CS@SiO2 particles for selective recognition of naringin

Molecularly imprinted polymers are being proposed for the development of novel biorecognition elements for active components. In this study, an imprinted chitosan coated silica nanoparticles (I‐CS@SiO₂) polymer was prepared by a simple procedure, in which, naringin (NG) with antioxidant activity, acted as a template, silica as a matrix and CS as a functional polymer. The binding properties were discussed by the equilibrium binding experiment method. Experiments show that the adsorption characteristics of I‐CS@SiO₂ are better than that of nonimprinted polymer. It exhibited high selectivity for NG when compared with the nonimprinted polymer, with an imprinting factor α of 1.74. Scatchard analysis of the I‐CS@SiO₂ indicated that there was a class of binding sites during the I‐CS@SiO₂ recognizing NG: The dissociation constant of K_D is 0.016 mmol L^?1, the maximum apparent binding capacity of B_max is 6.56 μmol g^?1. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40491.     

磁性粉煤灰空心微珠表面印迹聚合物选择性识别头孢氨苄

利用共沉淀法制备了粉煤灰空心微珠磁性复合材料（MFACs）,以乙烯基改性的MFACs为基质材料,利用乳液聚合法制备磁性粉煤灰空心微珠表面印迹聚合物（MMIPs）。通过SEM、FT-IR、TGA、XRD和VSM等方法对其物理化学性质进行表征,其比表面积123.65 m²·g^-1,且具有较好的热稳定性、超顺磁性（M_s=12.155 emu·g^-1）。通过系列吸附实验研究表明,Langmuir等温模型能较好地拟合MMIPs对头孢氨苄（cefalexin,CFX）的吸附平衡数据,25℃时MMIPs的单分子层吸附容量为69.55 mg·g^-1。准二级动力学模型能较好地描述MMIPs对CFX吸附动力学行为,选择性实验研究表明,MMIPs对CFX具有较好地选择识别性。结合高效液相色谱分析技术,MMIPs已成功应用于环境样品中痕量CFX的分离/富集。     

A new microemulsion approach for producing molecularly imprinted polymers with selective recognition cavities for gallic acid

Bulk and microemulsion systems were studied in order to obtain molecularly imprinted copolymers selective for gallic acid. Both systems contained acrylic acid as the functional monomer and ethylene glycol dimethacrylate as crosslinker. Microemulsion formation was confirmed by refractive index measurements and by conductivity analyses. Simple uptake tests revealed higher affinities for the microemulsion polymers; a 3.55 imprinting factor and a 0.275 g gallic acid (g polymer)^–1 adsorption capacity were recorded. Competitive uptake tests, from an oak bark extract, were in agreement with the simple uptake results and BET analyses. Microemulsion polymer particles selectively bind 4.58 times more gallic acid molecules relative to other competitor species.     

Molecularly imprinted polymers for the selective recognition of l‐phenylalanine based on 1‐buty‐3‐methylimidazolium ionic liquid

To enhance the affinity of 4‐vinyl pyridine to l ‐phenylalanine (l ‐Phe) and convert the imprinting process from the aqueous phase to the organic phase, an oil‐soluble amino acid ionic liquid was introduced as a template. In this study, 1‐butyl‐3‐methylimidazolium α‐aminohydrocinnamic acid salt was first applied to prepared surface molecularly imprinted polymers (MIPs) in acetonitrile for the selective recognition of l ‐Phe. Fluorescence quenching analysis of the functional monomer on the template was investigated under different conditions to study the imprinting mechanism. Several binding studies, such as the sorption kinetics, sorption thermodynamics, and solid‐phase extraction application, and the chiral resolution of racemic phenylalanine were investigated. The binding isotherms were fitted by nonlinear regression to the Freundlich model to investigate the recognition mechanism. The affinity distribution analysis revealed that polymers imprinted by ionic liquid showed higher homogeneous binding sites than those imprinted by l ‐Phe. The competition tests were conducted by a molecularly imprinting solid‐phase extraction procedure to estimate the selective separation properties of the MIPs for l ‐Phe. The target MIP was shown to be successfully for the separation of l ‐Phe from an amino acid mixture. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42485.     

Effect of electrostatic functional monomers on lysozyme recognition by molecularly imprinted hydrogel

Electrostatic functional monomers (EFMs) play an important role in noncovalent molecular imprinting due to their formed complexes with the complementary segment(s) of the template molecule. In this work using UV difference spectroscopy, interaction saturations of methacrylic‐acid and 2‐dimethyl‐amino‐ethyl‐methacrylate in complex formation with lysozyme (Lyz) surface was found to occur at molar ratios to Lyz of 400 and 100, respectively. Based on these results and the estimated free to total EFMs ratios, four sets of imprinted/nonimprinted hydrogel samples were synthesized alongside the two sets based on lysozyme surface charges and equal EFMs. Comparisons showed that the highest absorption capacity of 59 mg/g and imprinting effect of 1.58 correspond to samples with EFM/Lyz ratios at saturation and minimum free to total EFM/Lyz ratios, respectively. Minimization of free monomers is hence important in recognition of proteins by avoiding the nonspecific binding. This can have generic application for specific separation of other macromolecules. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41366.     

Surface molecularly imprinted polymers based on yeast prepared by atom transfer radical emulsion polymerization for selective recognition of ciprofloxacin from aqueous medium

To achieve selective recognition of water‐soluble ciprofloxacin (CIP), an effective method was developed for the preparation of surface molecularly imprinted polymers based on the yeast particles (yeast@MIPs) via atom transfer radical emulsion polymerization (ATREP). The reactions were carried out in the nontoxic and green emulsion system at room temperature, which was environment friendly with low energy consumption. In this study, the yeast, for the advantages of low cost, easily available source and abundant active groups on the cell wall, was selected as an ideal biological support substrate. The prepared yeast@MIPs was characterized by FT‐IR, SEM, TEM, EDS, and elemental analysis techniques. Batch mode adsorption studies were carried out to investigate the specific adsorption equilibrium, kinetics, selective recognition, and reuse ability of yeast@MIPs. The experimental static adsorption data of CIP on to yeast@MIPs were well‐described by Langmuir, Freundlich, and pseudo‐second‐order models. The maximum static adsorption capacity for CIP of yeast@MIPs was 18.48 mg g^?1, and the adsorption equilibrium could be reached in 60 min. The selectivity coefficients for CIP relative to enrofloxacin, tetracycline, and sulfadiazine were 1.212, 2.002, and 10.65, which demonstrated CIP of high affinity and selectivity over three competitive antibiotics. In addition, the reusability of the material without obvious deterioration (8.52% loss) in performance was observed at least four repeated cycles. And the yeast@MIPs was used to determine CIP from spiked shrimp samples by HPLC analysis. These results showed that yeast was a well‐defined substrate and ATREP was a promising technique for the preparation of surface molecularly imprinted polymers targeting templates. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40310.     

Binding and recognition ability of molecularly imprinted polymer toward p-nitrophenol

p-Nitrophenol is a hazardous phenolic compound and its separation and determination is very necessary to protect public health and environmental quality. In this article, macromolecule polyethyleneimine (PEI) grafted on the surface of silica particles was crosslinked using p-nitrophenol as a template and diepoxyalkyl (669) as a crosslinking agent, and molecularly imprinted polymer on the surfaces of silica gel MIP-PEI/SiO₂ was prepared. The binding and recognition ability of MIP-PEI/SiO₂ for p-nitrophenol were researched using batch and dynamic methods. The experimental results showed that MIP-PEI/SiO₂ had high affinity, specific recognition ability, and excellent selectivity for p-nitrophenol. The saturated binding amount could reach to 155.5 mg g⁻¹. The selectivity coefficients relative to m-nitrophenol and chlorophenol were 45.80 and 117.5, respectively. The empirical Freundlich isotherm was found to describe well the equilibrium binding data. pH of sample solution was found to have a strong influence on the binding amount. MIP-PEI/SiO₂ was regenerated easily using diluted hydrochloric acid solution as eluent and MIP-PEI/SiO₂ possesses better reusability. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of novel photoresponsive molecularly imprinted polymer microspheres with special binding properties

An azobenzene‐containing molecularly imprinting polymer microsphere with photoresponsive binding properties toward 2,4‐dichlorophenoxyacetic acid (2,4‐D) was successful prepared via silica surface polymerization. The number‐average diameters of silica and imprinting polymer microsphere are 0.5 and 0.7 μm, respectively. The static adsorption, binding and selectivity experiments were performed to investigate the adsorption properties and recognition characteristics of the polymers for 2,4‐D. The equilibrium adsorptive experiments indicated that 2,4‐D‐SMIP(surface molecularly imprinted polymers) has significantly higher adsorption capacity for 2,4‐D than its nonimprinted polymers (SNIP).The binding constant K_d and apparent maximum number Q_max of the imprinted polymer were determined by Scatchard analysis as 0.054 mmol L^?1 and 0.167 mmol g^?1_, respectively. The result of photoregulated release and uptake of 2,4‐D experiment demonstrated that azo‐containing SMIP can make use of light and change it into mechanical properties to release and take up the template molecules. It means that the SMIP can be controlled by light. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 869‐876, 2013     

Adsorption and recognition properties of ionic imprinted polyamine IIP‐PEI/SiO2 towards Pb2+ ion

In this article, an ionic imprinted polyamine (IIP) grafted on the surface of silica gel was prepared through a new surface imprinting approach. The adsorption and recognition properties of IIP‐PEI/SiO₂ for Pb²⁺ ion were studied in detail using batch rebinding studies. The experimental results showed that the IIP‐PEI/SiO₂ had high affinity, specificity, and selectivity for the template ion. The isothermal adsorption data was fit using the Langmuir equation. The adsorption was typical of chemisorption of a monolayer. The selectivity coefficients relative to Zn²⁺ and Cr³⁺ were 32.43 and 68.36, respectively. pH and temperature were found to have a strong influence on the adsorption properties. The adsorption amount increases with rising of temperature and the value of ΔH is plus. The adsorption of Pb²⁺ by IIP‐PEI/SiO₂ was spontaneous and endothermic. At pH = 7, the adsorption capacity of the polymers was the highest. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparative analysis of atrazine molecularly imprinted polymers using acetonitrile and toluene as solvents

Acetonitrile and toluene are solvents commonly used for the synthesis of atrazine molecularly imprinted polymers (MIPs), but their effects have seldom been compared in the same imprinting system. In this paper, effects of the two solvents in an atrazine molecular imprinting system were evaluated theoretically and experimentally. A polarizable continuum model was adopted, and it was found that using the two solvents, the energy difference for the atrazine–methacrylic acid complex between vacuum and solution was not the same. The two types of MIPs prepared using different solvents vary in morphology, porosity, binding capacity, and specificity. All of these results suggest that the abilities of the solvents used to form hydrogen bonds with other compounds in the system are different. The porogen imprinting effect of the solvents also has an influence on binding capacity. Compared to MIPs synthesized using acetonitrile as solvent (MIPs-ACN), MIPs synthesized using toluene as solvent (MIPs-PhMe) have fewer but larger pores and exhibit much higher adsorption capability but less rigorous specificity. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47190.     

Preparation of molecularly imprinted polymers for recognition and extraction of benzoylureas from apple samples

ABSTRACT

In this work, diflubenzuron (DBZ) molecularly imprinted polymers (MIPs) were synthesized by precipitation polymerization. The polymers were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), dynamic light scattering (DLS). The influences of synthetic conditions including template molecules, functional monomers and crosslinker on the surface morphology, particle size and size distribution of polymers were investigated. Scatchard analysis indicated the presence of specified recognition sites in MIPs. The Sips model was fitted better to the equilibrium data of MIPs over whole concentrations. The pseudo-second-order kinetic model was well fitted to the experimental data of adsorption kinetic experiment, suggesting the chemisorption mechanism between MIPs and DBZ. Four structurally similar compounds were used for the selectivity test of MIPs. It was observed that MIPs can selectively rebind the template molecules (DBZ) under the interference of four other structurally similar compounds. The application of MIPs in solid-phase extraction (SPE) offers a method for extraction and determination of benzoylureas (BUs) pesticides in apple samples prior to high-performance liquid chromatography (HPLC) analysis.