Preparation and performance valuation of high selective molecularly imprinted polymers for malachite green

Molecular imprinting is a technology that facilitates the production of artificial receptors toward compounds of interest. In this study, we prepared a series of molecularly imprinted polymers (MIPs) by precipitation polymerization for the purpose of binding specifically to malachite green (MG). The presence of monomer–template solution complexes in non-covalent MIPs systems had been verified by UV-spectrometric detection and molecular dynamics simulations. The synthesized parameters were, respectively, optimized and the optimal conditions for the efficient adsorption property were as follows: template: MG, 1 mmol; functional monomer: methacrylic acid (MAA), 8 mmol; cross-linker: ethylene glycol dimethacryllate, 16 mmol; and porogen: acetonitrile, 30 mL. Fourier transform infrared spectroscopy and nitrogen adsorption experiments were used to characterize the MIPs. Scatchard analysis was used for estimation of the dissociation constants and maximum amounts of binding sites. The polymer based on MAA had two classes of heterogeneous binding sites characterized by two values of K _D and B _max: K _D = 14.10 μmol L^?1 and B _max = 1.37 μmol g^?1 for the higher affinity binding sites, and K _D = 384.62 μmol L^?1 and B _max = 24.77 μmol g^?1 for the lower affinity binding sites. The specificity of MIPs on SPE column was evaluated by rebinding the other structurally similar compounds. The results indicated that the imprinted polymers exhibited an excellent stereo-selectivity toward MG.     

Selective solid-phase extraction of bisphenol A using molecularly imprinted polymers and its application to biological and environmental samples

Molecularly imprinted polymers (MIPs) were prepared using bisphenol A (BPA) as a template by precipitation polymerization. The polymer that had the highest binding selectivity and ability was used as solid-phase extraction (SPE) sorbents for direct extraction of BPA from different biological and environmental samples (human serum, pig urine, tap water and shrimp). The extraction protocol was optimized and the optimum conditions were as follows: conditioning with 5 mL methanol–acetic acid (3:1), 5 mL methanol, 5 mL acetonitrile and 5 mL water, respectively, loading with 5 mL aqueous samples, washing with 1 mL acetonitrile, and eluting with 3 mL methanol. MIPs can selectively recognize, effectively trap and preconcentrate BPA over a concentration range of 2–20 μM. Recoveries ranged from 94.03 to 105.3 %, with a relative standard deviation lower than 7.9 %. Under the optimal condition, molecularly imprinted SPE recoveries of spiked human serum, pig urine, tap water and shrimp were 65.80, 82.32, 76.00 and 75.97 %, respectively, when aqueous samples were applied directly. Compared with C18 SPE, a better baseline, better high-performance liquid chromatography separation efficiency and higher recoveries were achieved after molecularly imprinted SPE.      

2-异戊基环戊酮虚拟模板印迹微球的制备及其吸附性能

以2-异戊基环戊酮为虚拟模板,采用沉淀聚合法制备了粒径20~50 μm的分子印迹微球。 用傅里叶变换红外光谱(FTIR)和扫描电子显微镜(SEM)研究了分子印迹微球的表面化学特征及粒径分布,测试了印迹聚合物对玫瑰醚的吸附动力学、等温吸附性能及吸附选择性。 考察了分子印迹固相萃取玫瑰醚的应用效能。 结果表明:分子印迹聚合物(MIPs)对玫瑰醚的吸附可在25 min达到平衡,具有较快的吸附动力学,一级动力学模型更适合描述其吸附动力学行为。 Freundlich模型最适合描述MIPs对玫瑰醚的等温吸附行为,聚合物材料最大的印迹位点数目为149.3 μmol/g。 聚合物对玫瑰醚的平均吸附能为166 kJ/mol,表明主要为化学吸附。 虚拟模板印迹聚合物对玫瑰醚的选择因子相对于香叶醇和香茅醇分别为3.710和5.636,且对含玫瑰醚的混合物中的目标化合物仍具有较高的选择吸附能力(竞争吸附量为18.02 mg/g)。 在优化洗涤(1 mL乙腈+1 mL乙腈和水混合溶剂(体积比9.5:0.5)+2 mL乙腈、甲醇和水混合溶剂(体积比8:1:2)和洗脱(3 mL甲醇和醋酸混合溶剂(体积比9:1))条件下,通过分子印迹固相萃取可实现玫瑰醚的有效分离和富集,回收率为96.23%。     

Citrinin selective molecularly imprinted polymers for SPE

Molecularly imprinted polymers (MIPs) for citrinin (Cit) with 1‐hydroxy‐2‐naphthoic acid (HNA) as mimic template were prepared and the molecularly imprinted SPE method was developed for the detection of Cit in rice with HPLC. The adsorption properties of HNA and Cit on the MIPs and nonimprinted polymers were investigated. It proved that MIPs showed higher selectivity adsorption to HNA and Cit than nonimprinted polymers were. The recoveries of Cit in rice were in the range of 86.7–97.7%. The spiked rice samples and five rice samples in Beijing market were detected using molecularly imprinted SPE method and satisfied results were obtained as discussed in this article.     

印迹分子聚合物结合低共熔溶剂用于山楂中咖啡酸的固相萃取

在相同的实验条件下,分别合成了以咖啡酸为模板的印迹分子聚合物和无模板分子聚合物。使用场发射扫描电镜法和吸附实验表征这两种聚合物材料的孔状结构和选择性吸附性能。然后利用印迹分子聚合物、无模板分子聚合物、C₁₈萃取小柱这3种材料结合固相萃取法纯化山楂提取物中的咖啡酸,提取率分别为3.46、1.01、1.17 μg/g。为了优化固相萃取过程,实验研究了不同洗脱剂的影响。分别利用用氯化胆碱和甘油、氯化胆碱和尿素(摩尔比均为1:2)合成出两种低共熔溶剂。甲醇与这两种低共熔溶剂分别以不同的体积比混合作为洗脱剂,用于优化咖啡酸的固相萃取过程。实验结果表明,印迹分子聚合物是一种良好的固相萃取材料;当甲醇和甘油基低共熔溶剂在体积比为3:1混合时,表现出最好的洗脱能力,得到咖啡酸的回收率为82.32%。     

Development and application of molecularly imprinted polymers as solid-phase sorbents for erythromycin extraction

Six molecularly imprinted polymers (MIPs) of erythromycin (ERY) were prepared by noncovalent bulk polymerization using methacrylic acid (MAA) as the functional monomer. On the basis of binding analysis, the MIPs with 1:2 optimum ratio of template to MAA were selected for subsequent scanning electron microscopy and Brunauer–Emmett–Teller analyses, which indicated that the MIPs had more convergent porous structures than the nonimprinted polymers. The equilibrium binding experiments showed that the binding sites of MIPs were heterogeneous, with two dissociation constants of 0.005 and 0.63 mg mL⁻¹, respectively. Furthermore, the performance of the MIPs as solid-phase extraction (SPE) sorbents was evaluated, and the selectivity analysis showed that the MIPs could recognize ERY with moderate cross-reactivity for other macrolides. The overall investigation of molecularly imprinted SPE for cleanup and enrichment of the ERY in pig muscle and tap water confirmed the feasibility of utilizing the MIPs obtained as specific SPE sorbents for ERY extraction in real samples. Figure Schematic diagram of the preparation and application of the erythromycin imprinted molecularly imprinted polymers Suquan Song and Aibo Wu contributed equally to this work.     

Comparative study of capsaicin molecularly imprinted polymers prepared by different polymerization methods

In this study, the molecularly imprinted polymers (MIPs) of capsaicin are prepared by bulk polymerization (MIPs1), precipitation polymerization (MIPs2), and surface imprinting technology based on SiO₂/Fe₃O₄ particles (MIPs3), respectively. MIPs are characterized by scanning electron microscopy and fourier transform infrared spectroscopy. The adsorption kinetics and thermodynamics of these composites are also investigated to estimate their capacity to rebind capsaicin. The adsorption kinetics show that the adsorption process of MIPs1 is fitted to pseudo first‐order kinetic model, while the kinetic properties of MIPs2 and MIPs3 are well described by pseudo second‐order kinetic model. Adsorption thermodynamics analysis indicated that there are two kinds of binding sites with different affinity in each MIPs, whereas only one kind of binding site in non‐imprinted polymers. All adsorption isotherms of MIPs are fitted to Freundlich models, illustrated that binding sites are distributed heterogeneously in the surface of the materials, and the adsorption might occur in the multimolecular layers. Comparisons of experimental data of three MIPs are achieved and the results show that MIPs3 has the best affinity and absorption capacity to capsaicin. Moreover, the MIPs3 maintain the magnetic properties of Fe₃O₄ particles, which will be applied to the rapid separation of capsaicin from chili peppers samples. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 157–164     

合成引发方式对槲皮素-钴(Ⅱ)配位印迹聚合物结构与性能的影响

以槲皮素-钴(Ⅱ)的配合物为模板分子,在强极性甲醇溶剂中分别采用低温光引发和高温热引发聚合制备槲皮素-钴(Ⅱ)配位印迹聚合物.紫外-可见光谱分析确定了槲皮素与钴(Ⅱ)形成配合物的最佳配位比.根据印迹聚合物的平衡结合量优化功能单体丙烯酰胺用量.利用红外光谱、透射电镜和平衡结合实验,考察不同引发方式对聚合物的结构、微观形貌及结合性能的影响.进一步通过特异吸附容量和印迹指数确定,低温光引发聚合更适于配位分子印迹聚合物的制备.同时研究了不同阳、阴离子对印迹聚合物选择识别性的影响.结果表明光引发的金属配位分子印迹聚合物具有良好的吸附选择性,印迹指数可达3.919.     

Selective solid-phase extraction of tebuconazole in biological and environmental samples using molecularly imprinted polymers

Molecularly imprinted polymers (MIPs) were prepared by precipitation polymerization using tebuconazole (TBZ) as a template. Frontal chromatography and selectivity experiments were used to determine the binding capabilities and binding specificities of different MIPs. The polymer that had the highest binding selectivity and capability was used as the solid-phase extraction (SPE) sorbent for the direct extraction of TBZ from different biological and environmental samples (cabbage, pannage, shrimp, orange juice and tap water). The extraction protocol was optimized and the optimum conditions were: conditioning with 5 mL methanol:acetic acid (9:1), 5 mL methanol and 5 mL water respectively, loading with 5 mL aqueous samples, washing with 1.2 mL acetonitrile (ACN):phosphate buffer (5:5, pH3), and eluting with 3 mL methanol. The MIPs were able to selectively recognize, effectively trap and preconcentrate TBZ over a concentration range of 0.5–15 μmol/L. The intraday and interday RSDs were less than 9.7% and 8.6%, respectively. The limit of quantification was 0.1 μmol/L. Under optimum conditions, the MISPE recoveries of spiked cabbage, pannage, shrimp, orange juice and tap water were 62.3%, 75.8%, 71.6%, 89% and 93.9%, respectively. MISPE gave better HPLC separation efficiencies and higher recoveries than C18 SPE and strong cation exchange (SCX) SPE. Figure HPLC analysis of spiked pannage after MISPE (A) and after C18 SPE (B). HQ (1), E3 (2), p-NP (3), FTF (4), TBZ (5), PNZ (6), HXZ (7) Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

分子印迹固相萃取-高效液相色谱法测定饲料中莱克多巴胺

以莱克多巴胺为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了对莱克多巴胺具有高选择性的分子印迹聚合物。考察了甲醇、乙腈、丙酮和氯仿-甲醇与三乙胺构成致孔剂合成的聚合物性能及其形貌特征。通过正交试验优化的聚合反应配方为: 1.0 mmol莱克多巴胺,4.0 mmol丙烯酰胺,20.0 mmol乙二醇二甲基丙烯酸酯,6.0 mL乙腈-三乙胺(30:1, v/v), 50.0 mg偶氮二异丁腈。建立的基于分子印迹固相萃取-高效液相色谱测定饲料试样中莱克多巴胺的方法,在0.50～100 mg/L质量浓度范围内有良好的线性关系(r=0.9994);饲料试样中1.0、10及100 mg/kg 3个添加水平的莱克多巴胺平均回收率大于80%;批内、批间测定的相对标准偏差小于10%;检出限(信噪比为3)达到0.1 mg/kg。该方法灵敏、可靠,用于饲料等复杂基质中莱克多巴胺检测的效果优于相关标准分析方法。     

Quercetin molecularly imprinted polymers: Preparation, recognition characteristics and properties as sorbent for solid-phase extraction

Molecular imprinted polymers (MIPs) were prepared through thermal polymerization by using quercetin as the template molecule, acrylamide (AA) as the functional monomer and ethylene glycol dimethacrylate (EDMA) as the cross-linker in the porogen of tetrahydrofuran (THF). The synthesized MIPs were identified by both Fourier transform infrared (FTIR) and scanning electron microscope (SEM). Systematic investigations of the influences of key synthetic conditions, including functional monomers, porogens and cross-linkers, on the recognition properties of the MIPs were conducted. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. Besides quercetin, two structurally similar compounds of rutin and catechol were employed for molecular recognition specificity tests of MIPs. It was observed that the MIPs exhibited the highest selective rebinding to quercetin. Accordingly, the MIPs were used as a solid-phase extraction (SPE) sorbent for the extraction and enrichment of quercetin in cacumen platycladi samples, followed by HPLC-UV analysis. The application of MIPs with high affinity and excellent stereo-selectivity toward quercetin in SPE might offer a novel method for the enrichment and determination of flavonoid compounds in the natural products.     

利用分子印迹技术预处理生物样品中头孢药物的研究

优化了头孢硫脒分子印迹聚合物的合成条件,探讨了分子印迹技术和固相萃取联用对血浆中头孢硫脒的分离富集,发现用4-乙烯基吡啶作功能单体合成的分子印迹聚合物作为固相萃取填充料,能定量吸附血浆中的头孢硫脒,并初步研究了其吸附机理。     

Molecular imprinting of natural flavonoid antioxidants: application in solid-phase extraction for the sample pretreatment of natural products prior to HPLC analysis

As shown in the past years, SPE based on molecularly imprinted polymers (MIPs) may provide significant enhancement of selectivity in sample preparation and analyte preconcentration. The objective of this work was the fabrication of MIPs for the specific adsorption of rutin and quercetin. The two flavonoids were used as the template molecules for the preparation of MIP phases in a self-assembly (noncovalent) approach. The produced MIPs were validated with regard to the imprinting efficiency as media for LC and SPE. The retention behavior of several flavonoid compounds was studied using as stationary phases imprinted, control nonimprinted polymers, and commercial silica-based materials. MIPs were applied as materials for the selective SPE and preconcentration of the flavonoids from white and red wine, orange juice, and tea. The collected fractions were analyzed by high-pressure LC. MIP-SPE facilitated specific analyte isolation and effective sample clean-up. The results show that molecularly imprinted SPE can be a useful tool for the simple, selective, and cost-effective pretreatment of samples containing natural antioxidants.     

Synthesis of molecularly imprinted polymer as a sorbent for solid phase extraction of bovine albumin from whey,milk, urine and serum

This study describes the synthesis of molecularly imprinted polymers (MIPs) using bovine albumin as a template, 2-VP as a functional monomer, EGDMA as a cross-linker and AIBN as an initiator by radical polymerization. Non-imprinted polymers (NIPs) were prepared and treated with the same method, but in the absence of bovine albumin. The synthesized MIPs and NIPs were characterized on the basis of FTIR, TGA and DTA. An adsorption process (solid phase extraction, SPE) for the removal of bovine albumin using the fabricated MIPs and NIPs was evaluated under various conditions. Effective parameters on bovine albumin retention for example, pH, flow rate, nature of the eluent, the ionic strength, selectivity coefficient, and retention capacity were studied. Competition test implicates that the MIP adsorbents have the strongest specific retention and enrichment for bovine albumin respect to NIPs. The maximum adsorption of bovine albumin by the fabricated MIPs was 24 mg/g. The calibration curves were linear in the range of 20–200 mg/L of bovine albumin. The limit of detection (LOD), the calibration sensitivity, the relative standard deviation (RSD) and preconcentration factor under optimal experimental conditions were 2.44 and 25, respectively. The extraction of bovine albumin from blood serum, urine, whey and milk samples had a selectivity and enrichment property. In the actual experiment for real samples, recovery of ~ 80% was achieved.     

Design,synthesis, and characterization of molecularly imprinted solid phase extraction for alpha Mangostin analysis in blood sample

Low levels of α-mangostin (AM) in biological fluids require adequate sample preparation to be analyzed. Molecularly imprinted polymers can serve as sorbents in solid phase extraction, enabling concentration and extraction of α-mangostin from complex matrices, such as biological fluids. To date, there are no molecular imprinted polymers for the analysis of α-mangostin in biological fluids. In this study, AM molecular imprinted polymer (MIP) was designed using molecular modeling, molecular dynamic simulations, and prepared by bulk polymerization and suspension polymerization methods. The geometry optimization results showed that acrylamide (AAM) monomer forms the most stable complex with AM at the pre-polymerization with the most negative Gibbs free energy (ΔG) of −6.91818 Kcal/mol. Radial distribution function (RDF) in molecular dynamics simulation of AM:AAM:ethylene glycol dimethacrylate (EGDMA) with mol ratio 1:4:20 shows the complex with the best composition through the formation of four stable hydrogen bonds. Based on the experimental results, molecularly imprinted polymers in suspension exhibit better characteristics, selectivity, and adsorption capacity than in bulk. The suspension polymerization method showed a high recovery (85.88% ± 2.5), which was higher than C18 SPE cartridge (24.19% ± 1.47). Hence, it can be concluded that the MIPs from MD simulations were accessible and could be used in practice, such as in the separation and detection of AM in blood serum.     

分子印迹固相萃取-高效液相色谱法测定猪肉中红霉素残留

采用沉淀聚合法,以红霉素（erythromycin,ERY）为模板,甲基丙烯酸（methacrylic acid,MAA）为功能单体,乙二醇二甲基丙烯酸酯（ethyleneglycoldimethacrylate,EGDMA）为交联剂,甲醇/乙腈（1:4,v/v）为致孔剂制备了ERY分子印迹聚合物（molecularly imprinted polymers,MIPs）。通过扫描电镜、平衡吸附实验等对制备的印迹和非印迹聚合物进行表征和测定,结果表明所制备的MIPs对ERY具有特异性吸附作用。Scatchard分析证明MIPs对ERY的吸附存在两类不同结合位点,最大表观结合量（Q_max）和平衡解离常数（K_d）分别为Q_max1=45.24 mg/g,K_d1=0.028 g/L; Q_max2=87.53 mg/g,K_d2=0.20 g/L。以制备的MIPs为吸附剂的分子印迹固相萃取柱,结合高效液相色谱法能够快速检测猪肉样品中的ERY残留,线性范围为0.5~50 mg/L（r²=0.9994）,检出限（S/N=3）为0.2 mg/kg。猪肉样品中不同添加水平下ERY的加标回收率为95.2%~104.2%,相对标准偏差（RSD）小于5%。该方法选择性好,灵敏、可靠,可用于猪肉等复杂食品样本中ERY残留的检测。     

双酚F分子印迹聚合物的制备及其对水相中双酚F吸附性能的研究

以双酚F(4,4′-BPF)为模板分子,α-甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用沉淀聚合法合成4,4′-BPF分子印迹聚合物(MIPs)。运用傅里叶红外(FT-IR)光谱对产物的结构进行表征,并对其吸附等温线、吸附动力学、吸附热力学及选择性识别性能进行研究。结果表明:MIPs对水相中4,4′-BPF具有特异性吸附,最大吸附容量为82.8 mg/g;Freundlich模型拟合吸附等温线的相关系数R2=0.995;热力学参数ΔG、ΔS、ΔH均小于0,表明此吸附过程是自发进行的、熵减的、放热的。     

Molecularly imprinted polymers microsphere prepared by precipitation polymerization for hydroquinone recognition

A one-step precipitation polymerization synthesis was adopted for the preparation of molecularly imprinted polymers (MIPs) by using hydroquinone as a template molecule. The transmission electron microscopy (TEM) exhibited that the polymers were uniform spheres with the diameter of about 700 nm. The results of adsorption experiments showed that the microspherical imprinted polymers possessed fast adsorption dynamics. Compared to the structurally similar compounds, catechol and resorcinol, the MIPs exhibited a high recognizable capacity to hydroquinone. And the electrochemical sensor fabricated by modifying the prepared MIPs microsphere on the glassy carbon electrode surface was used to detect the hydroquinone concentration. The current response was proportional to the concentration of hydroquinone in the range of 2.0 x 10(-6) to 1.0 x 10(-4)mol/L with the detection limit of 1.0 x 10(-6)mol/L.     

非那西汀印迹聚合物固相萃取性能研究

研究非那西汀分子印迹聚合物的固相萃取性能。用本体聚合法制备非那西汀分子印迹聚合物,通过静态平衡吸附试验及固相萃取试验,研究其固相萃取性能。非那西汀模板聚合物的吸附能力明显强于空白聚合物。模板聚合物对浓度为0.03mmol/L的非那西汀标准溶液一次性萃取率为74.2%。非那西汀印迹聚合物对非那西汀具有特异性识别性能,可作为固相萃取固定相的应用研究。     

Molecularly imprinted polymers for bisphenol A for HPLC and SPE from water and milk

Molecularly imprinted polymers (MIPs) for bisphenol A (BPA) were prepared by two synthetic routes: semi-covalent and noncovalent methodology. The molecular imprinting effect was evaluated using the polymers in HPLC and SPE. Polymers prepared with noncovalent mode were proven more effective. These polymers were applied in SPE facilitating selective retention of BPA from bottled water and milk. The developed sample preparation was simple and efficient comprising only dilution of milk and MISPE prior to LC-MS analysis. Overall MISPE enhanced sample clean-up. Compared with control nonimprinted polymers and conventional C18 SPE cartridges, the MIPs exhibited selective analyte recognition. The method provided quantitative BPA recoveries, very good reproducibility (% RSDs lower than 7%), and low LOD (0.2 ng/g). MIP interacts similarly with deuterated BPA allowing its use as internal standard in LC-MS. The most critical parameters of MISPE were the organic content in loading-washing medium and the washing volume. Low flow rates in the elution step enhanced extraction recovery. Important advantages of the MIP were: the high breakthrough volumes (> 500 mL of water), high mass capacity (> 10 ng/mg of MIP sorbent), good linearity, and good stability in performance for over 35 cycles of use.