Using molecularly imprinted polymer for protecting functional group in organic reaction

In this study, a novel method of selective protecting group based on molecularly imprinted polymer for regioselective organic reaction is reported. The simplicity, convenience and feasibility of this method may be illustrated by the protection of hydroxyl group at C17 or C3 of β‐estradiol in the reaction between β‐estradiol and diphenylphosphinic chloride. Polymers to protect hydroxyl group at C17 or at C3, both demonstrated excellent protection effect. In polymers imprinted with 2‐methyl‐cyclopentanol template to protect hydroxyl group at C17, the proportion of 3‐phosphate was almost as high as 100%. In molecularly imprinted polymer synthesized using 5,6,7,8‐Tetrahydro‐2‐naphthol as a template to protect hydroxyl group at C3, the proportion of 17‐phosphate reached 98.2%. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

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.     

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.     

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     

杨梅黄素分子印迹聚合物的制备及其识别性能研究

以杨梅黄素(MYR)为模板分子、2-乙烯基吡啶(2-VP)为功能单体、二甲基乙二醇丙烯酸酯(EDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,甲醇为致孔剂,采用分子印迹技术制备了杨梅黄素分子印迹聚合物(MYR-MIP)。通过红外光谱、扫描电镜、热重分析等技术表征了MYR-MIP的理化性能;采用紫外光谱分析研究了MYR-MIP对MYR的等温吸附和动力学吸附特性,研究结果表明MYR-MIP对MYR具有良好的特异性吸附,并且在2 h内达到平衡吸附;高效液相色谱分析表明MYR-MIP对MYR具有优良的选择识别特性。     

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.     

Surface molecularly imprinted polymer prepared by reverse atom transfer radical polymerization for selective adsorption indole

The preparation of indole molecularly imprinted polymers (indole‐MIPs) using 4‐vinylpyridine as functional monomer, silica gel as matrix were used to adsorb indole from fuel oil specifically. The reverse atom transfer radical polymerization (RATRP) technology was introduced to prepare the surface molecularly imprinted polymers, and the precipitation polymerization was adopted in the preparation process. The obtained indole‐MIPs were characterized by nitrogen adsorption, Fourier transform infrared spectrometry and scanning electron microscopy. The results show that indole‐MIPs were provided with the larger surface areas and more pores. The adsorption capacity of indole‐MIPs was 31.80 mg g^?1 at 298 K, and the adsorption equilibrium was reached in a short time. The adsorption process was spontaneous by thermodynamic analysis, and an appropriate decrease in temperature could enhance the adsorption capacity. The adsorption process obeyed pseudo‐second‐order kinetic model by kinetics analysis. The isotherm analysis results show that both Langmuir and Sips equations were suitable to experimental data. The selective adsorption and reusable performance of indole‐MIPs were favorable. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40473.     

表面分子印迹材料制备研究进展

表面分子印迹技术是通过把分子识别位点建立在印迹材料的表面,来提高识别位点与印迹分子的结合速度,进一步加强印迹材料吸附分离效率。从无机硅胶材料和聚合物材料两方面综述了表面分子印迹材料制备技术发展现状,着重评述了表面分子印迹聚合物微球的制备方法及相应产品的性能,并指出表面分子印迹技术存在的不足。     

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     

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.     

Preparation of molecularly imprinted polymer films on monodisperse macromolecular beads

A new and facile technique for preparing homogeneous and highly selective molecularly imprinted polymers (MIPs) films on porous monodisperse poly‐(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) beads (P_GMA‐EDMA beads) has been described: before polymerization, initiator was immobilized on the P_GMA‐EDMA beads' surface by chemical reactivity; then functional monomers and crosslinkers were initiated by the surface‐bound initiator and copolymerized to form MIPs films on the P_GMA‐EDMA beads' surface in the presence of template molecules. The resulting beads were analyzed by FTIR spectroscopy and X‐ray photoelectron spectra. The effects of the initiator amount and copolymerization time on the content of MIPs, and MIPs contents on morphologies and pore properties of the resulting beads were investigated. The results show that the content of MIPs can be adjusted by changing initiator amount or by controlling copolymerization time. The binding experiments indicate that, at lower grafting level, with the increase of MIPs content, the adsorption and recognition capabilities of the resulting beads enhance. When MIPs content increase to 16.75%, the highest adsorption and recognition capabilities are obtained. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of molecularly imprinted polymer of bovine serum albumin

Molecularly imprinted polymer beads of bovine serum albumin (BSA) were prepared via inverse phase suspension polymerization, using BSA as the template molecule, a combination of acrylamide and methacrylic acid (MAA) as double functional monomers, and N, N′‐methylene bisacrylamide as the crosslinker. The effect of different monomer ratios and degrees of crosslinking were investigated. When both selectivity and physical properties of the resultant polymer beads were taken into account, the ratio of MAA in the total monomers was chosen at 40% (m/m) and the degree of crosslinking at 30% (n/n), the resultant polymer beads had good selectivity (α = 2.77) and good physical properties. The effects of pH and temperature were studied. It turned out that the functionalization of polymers of BSA prepared via inverse‐phase suspension polymerization exhibited specific recognition for BSA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

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.     

Influence of polymer morphology on the adsorption behaviors of molecularly imprinted polymer‐methacrylic acid functionalized β‐cyclodextrin

The influence of molecularly imprinted polymer‐methacrylic acid functionalized β‐cyclodextrin (MIP(MAA‐β‐CD)) morphology on the adsorption behavior studies towards benzylparaben (BzP) was explored. The effects of time, concentration, and temperature towards BzP uptake were extensively evaluated. The adsorption performance of MIP(MAA‐β‐CD) was compared with that on the molecularly imprinted polymer‐methacrylic acid (MIP(MAA)) synthesized without β‐CD. The MIP(MAA‐β‐CD) was synthesized to obtain a spherical and spongy‐porous texture with a broad pore size distribution. The MIP(MAA‐β‐CD) showed fast kinetic and the intra‐particle diffusion model demonstrated a three step (surface and pore) adsorption process. The Koble‐Corrigan isotherm was the most suitable model for data fitting, which indicated that MIP(MAA‐β‐CD) had homogeneous and heterogeneous surfaces. This finding clearly demonstrated that the large uptake and strong affinity of MIP(MAA‐β‐CD) did not only probably result from the monomer‐template interactions, but also due to the morphological MIP(MAA‐β‐CD) structure. In contrary to MIP(MAA‐β‐CD), MIP(MAA) synthesized with uniform morphology and narrow pore size distribution had lower adsorption capacities and its kinetic data fitted the pseudo‐second order diffusion model, indicating a two‐step (surface only) adsorption process. The MIP(MAA) adsorption process followed the Langmuir isotherm model referred to solely homogeneous uptake. The calculated thermodynamic parameters showed that the BzP uptake was exothermic, spontaneous, and physisorption process onto MIPs, which supported the results of kinetics and isotherm adsorption data. This study clearly revealed that the presence of β‐CD improved the morphology of synthesized MIP, and automatically enhanced the adsorption behavior of MIP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42720.     

Studies on the preparation and properties of inorganic molecularly imprinted polymer (MIP) based on tetraethoxysilane and silane coupling agents

Inorganic molecularly imprinted polymer (MIP) based on tetraethoxysilane (TEOS), methyl triethoxysilane (MTEOS), and phenyl triethoxysilane (PTEOS) by sol‐gel process has been developed. The MIP's preparation conditions, H₂O/Si molar ratios (R), template removal procedures, calcination temperatures, and quantity of ammonium hydroxide were investigated. The competition experiments of the MIP for template (caffeine, CAF) and analogue (theophylline, TH) were analyzed by high‐performance liquid chromatography (HPLC). The results showed that the Ad_CAF decreased with an increase of the H₂O/Si molar ratios, but the selectivity (α) increased with an increase of the H₂O/Si molar ratios in the MIP. In addition, in a comparison of the procedures for removing the template, calcination obtained better efficiency and higher selectivity than extraction. The optimum adsorption and selectivity of MIP were obtained with R = 10 and the template was removed by calcination at 600°C. Moreover, the selectivity of the MIP (283.9) was greater than the nonimprinted polymer (2.45) under optimum preparation conditions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Direct synthesis of surface molecularly imprinted polymers based on vinyl–SiO2 nanospheres for recognition of bisphenol A

Molecularly imprinted polymers (MIP) with high performance in selectively recognizing bisphenol A (BPA) were prepared by using a novel and facile surface molecular‐imprinting technique. Vinyl‐functionalized, monodispersed silica spheres were synthesized by a one‐step emulsion reaction in aqueous solution. Then, BPA surface molecularly imprinted polymers (SMIP) were prepared by polymerization with 4‐vinylpyridine as the functional monomer and ethylene glycol dimethacrylate as the crosslinker. Maximal sorption capacity (Q_max) of the resulting SMIP was up to 600 μmol g^?1, while that of nonimprinted polymers was only 314.68 μmol g^?1. Kinetic binding study showed that sorption capacity reached 70% of Q_max in 20 min and sorption equilibrium at 80 min. SMIP had excellent accessibility and affinity toward BPA, for the selectivity coefficients of SMIP for BPA in respect to phenol, p‐tert‐butylphenol, and o‐phenylphenol were 3.39, 3.35, and 3.02, respectively. The reusage process verified the SMIP owning admirably stable adsorption capacity toward BPA for eight times. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of cinchonine molecularly imprinted photonic crystal film and its specific recognition and optical responsive properties

The cinchonine molecularly imprinted photonic polymer (MIPP) film was prepared by using methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross linker, benzoyl peroxide and N,N‐dimethylaniline as initiation system by a combination of colloidal crystal template method and molecular imprinting technique. The structure and morphology of the polymer film were characterized by infrared spectra and scanning electronic microscope. The results exhibit that a highly ordered three‐dimensionally interconnected macroporous array with typical face‐centered cubic (fcc) structure was formed in the MIPP film. The binding experiments showed that the special, hierarchical porous structure enabled this polymer to possess rapid adsorption kinetics, improved binding capacity, and specificity to analytes. The Bragg diffractive measurements showed that the MIPP film has good specific responsiveness for the template molecules. The Bragg diffraction peaks shifted from 527 to 503 nm with the concentration of the cinchonine varying from 0 to 10^?3 mol/L, whereas there were no obvious peaks shifts for its structural analogues. This may be ascribed that the changes in the lattice constants and the average refractive indices of MIPP film caused by the special adsorption of template molecules toward recognition sites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43191.     

Synthesis of a perfluorooctanoic acid molecularly imprinted polymer for the selective removal of perfluorooctanoic acid in an aqueous environment

Perfluorooctanoic acid (PFOA) contamination in the environment is a global problem. The aqueous phase is the main medium for PFOA because of its moderate solubility. Adsorption is a feasible way to remove PFOA because of its chemical and biological stability. In this study, a new type of molecularly imprinted polymer (MIP) for the selective adsorption of PFOA in aqueous solutions was synthesized by the precipitation polymerization method with PFOA as the template molecule after optimization. The adsorption kinetics and isotherms of the MIP adsorbent toward PFOA were studied, and the effects of the pH and cations on the adsorption were investigated with batch experiments. The results show that acrylamide (AAM) was the best functional monomer, and the optimal molar ratio of PFOA to AAM to ethylene glycol dimethacrylate (crosslinker) was 1:6:25. The optimized MIP adsorbent had a high affinity for PFOA, and the uptake percentage by the MIP adsorbent was 1.3–2.5 times that of the nonimprinted polymer (NIP) when PFOA existed alone. A maximum PFOA sorption capacity of 5.45 mg/g based on the Langmuir isotherm model was achieved with the MIP adsorbent. The MIP adsorbent exhibited a high selectivity for PFOA over competitive compounds (other perfluorinated alkyl carboxylic and sulfonic acids), whereas the NIP did not. Approximately 90% of the PFOA in the mixture was removed by the MIP adsorbent; this was 18 times that of the NIP. Moreover, the regenerability of the MIP adsorbent was confirmed in five sequential adsorption–desorption cycles without a significant reduction in the PFOA uptake. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43192.