乙氧酰胺苯甲酯表面分子印迹聚合物的制备与吸附特性

合成功能单体N,O-双异丁烯酰乙醇胺（N,O-bismethacryloyl ethanolamine,NOBE）,采用表面分子印迹技术,以硅胶为载体,乙二醇二甲基丙烯酸酯（ethylene glycol dimethacrylate,EGDMA）为交联剂,制备乙氧酰胺苯甲酯（ethopabate,ETP）分子印迹聚合物（molecularly imprinted polymers,MIPs）。采用正交试验方法,对ETPNOBE物质的量比、ETP-EGDMA物质的量比和致孔剂种类3 个因素进行考察,结果表明：3 个影响因素主次顺序为致孔剂种类＞ETP-NOBE物质的量比＞ETP-EGDMA物质的量比;当致孔剂为乙腈、ETP-NOBE-EGDMA的物质的量比为1∶2∶20时,所制备的ETP-MIPs印迹效果最佳。Scatchard模型研究发现存在两类结合位点,高亲和位点与低亲和位点的平衡离解常数Kd和最大表观结合量Qmax分别为Kd1=1.608 μg/mL,Qmax1=1.101 μg/mg;Kd2=0.109 μg/mL,Qmax2=0.172 μg/mg。     

Preparation of estriol-molecularly imprinted silica nanoparticles for determining oestrogens in milk tablets

In this paper, the molecularly imprinted polymer layer of estriol at the silica nanoparticles surface with selective recognition had been constructed. The methacryl groups of functional monomer at the silica nanoparticles surface were acted as reactive sites to induce imprinting polymerisation. The absorption capacity results showed that the molecularly imprinted polymers had an excellent combining affinity, recognition selectivity and fast kinetics. Furthermore, the molecularly imprinted polymers were successfully used as absorbent of dispersive solid-phase extraction coupled with high-performance liquid chromatography to determinate trace estriol and estradiol in milk tablets. The high recoveries yielded of 89.1-93.5% were achieved with the relative standard deviations less than 9.4%. So, the molecularly imprinted polymers are the effective absorbents for the separation and enrichment of oestrogens in the complex matrices samples.     

Improving methods of analysis for mycotoxins: molecularly imprinted polymers for deoxynivalenol and zearalenone

Selective polymeric phases intended for future use in separation/extraction of deoxynivalenol and zearalenone from beverages have been prepared. Using crystalline deoxynivalenol, zearalenone and quercetin, molecularly imprinted polymers were obtained by a non-covalent imprinting approach via a photo-initiated addition polymerization. Prepared polymers were based on 4-vinylpyridine, methacrylic acid or 2-trifluoromethylacrylic acid as the functional monomer and on ethyleneglycol dimethacrylate, trimethyltrimethacrylate or divinylbenzene as the cross-linking monomer. Selectivity of the generated molecularly imprinted polymers has been investigated by application of the prepared molecularly imprinted polymers as stationary phases in high-pressure liquid chromatography experiments. The retention and elution behaviours of the template compounds and structurally related substances were determined and compared. The results promise future application of molecularly imprinted polymers as alternative selective matrices for clean-up and enrichment of deoxynivalenol and zearalenone.     

磁性表面分子印迹聚合物对食品中苏丹红Ⅰ的检测

本文研究了一种对苏丹红Ⅰ的检测的新方法,即磁性表面分子印迹技术。主要是以包裹二氧化硅的磁性纳米颗粒为载体,在其表面合成对苏丹红Ⅰ有特异性识别的磁性表面分子印迹聚合物。利用紫外分光光度计、红外光谱分析仪及透射电子显微镜对于所制备的苏丹红Ⅰ磁性分子印迹聚合物的磁性、形态学功能、吸附性能和特异性进行检测。实验结果表明该磁性表面分子印迹聚合物的印迹位点位于磁性载体的表层,提高与目标物质的结合能力。在外磁场条件下,磁性表面分子印迹聚合物能够轻松地达到吸附平衡并实现磁分离,降低非特异性吸附,从而提高对苏丹红Ⅰ的吸附量和选择性。最后对辣椒中含有的苏丹红Ⅰ进行了回收率检测,回收率达到80%以上。说明采用磁性表面分子印迹法对食品中苏丹红Ⅰ可快速、高效的检测。     

Preparation and Evaluation of Histamine Imprinted Polymer as a Selective Sorbent in Molecularly Imprinted Solid-Phase Extraction Coupled with High Performance Liquid Chromatography Analysis in Canned Fish

A series of molecularly imprinted polymers (MIPs) were prepared against histamine. Different template/monomer ratios were applied to optimize the imprinting condition. Methacrylic acid (MAA) as a functional monomer and Chloroform as a solvent were applied in polymerization process. The binding properties of MIPs were studied in comparison with a blank non-imprinted polymer. The optimized polymer, with a histamine/MAA ratio of 1/4, was selected as a sorbent in molecularly imprinted solid-phase extraction (MISPE) of histamine from canned fish. Scatchard analysis of MIP-histamine interactions revealed two types of binding sites for MIP: high affinity (K_D?=?11.11 μM) and low affinity (K_D?=?333.3 μM). The MISPE procedure was calibrated and a recovery of 76.5–97.6 % was obtained. The intra-and inter-day precision values were less than 5.70 % and 10.1 %, respectively. The selectivity of MISPE for histamine was also studied in comparison with some other structurally similar amines, which could be simultaneously present in canned fish. The performance of the imprinted polymer was examined and the results indicated that its good selectivity and affinity for histamine was very promising. Therefore, the proposed calibrated method could be applied in selective extraction and analysis of histamine in canned fish.     

分子印迹技术在新烟碱类农药残留分析中的应用研究进展

分子印迹技术(MIT)是基于主客体分子识别作用,以目标物为模板,合成具有专一识别性能的高分子聚合物的技术。分子印迹聚合物(MIPs)具有预定性特异性以及良好的实用性,能够有效解决传统样品前处理和分析检测中非特异性吸附问题,该技术已被广泛应用在新烟碱类农药的分离、富集和检测,提高了检测效率和准确度。本文以分子印迹聚合物为基础系统介绍了分子印迹聚合物的制备方法、新型材料在分子印迹技术中的应用,重点介绍了分子印迹技术在新烟碱类农药前处理和检测两个方面的应用,并对当前分子印迹技术进行了总结和展望。     

分子印迹技术在农药残留检测中的应用进展

分子印迹技术是一种由模板、功能单体和交联剂制备的高分子功能材料以展示其选择性分子识别行为的技术,因为其具有专一识别性、预定性和实用性等特点,广泛应用于农药残留检测中。本文概括了分子印迹技术的基础理论、分子聚合物的制备以及该技术在农药残留检测中的应用,其中主要包括分子印迹在固相萃取、色谱固定相、固相微萃取、分子印迹膜和传感器等方面的应用,并对其发展趋势进行了展望。近几年,分子印迹技术与磁性分子、纳米材料、荧光分子、传感器等应用技术结合,期待在分子印迹固有特异性识别带来的高灵敏度基础上,实现快速检测技术的突破,解决现有农残速测仪所测农药品种受限、假阳性高、定量难等缺点,真正实现高通量快速痕量检测。     

Approaches for the assembly of molecularly imprinted electrospun nanofibre membranes and consequent use in selected target recognition

Molecular recognition plays an indispensable role in nature for the recognition of antibodies, enzymes and nucleic acids. Biomimetic fibrous non-woven materials are being developed to act as highly sensitive and selective artificial receptors based on molecular recognition sites in the constituent fibres. Molecular imprinting technologies (MITs) with specific recognition abilities are currently being developed to produce versatile materials for the recognition of diverse species in various applications, but specifically in membrane separation to express permselectivity. Conventionally, the production of molecularly imprinted polymers (MIPs) involves introducing binding sites where highly cross-linked copolymers are formed around the analyte molecules that act as cavity-creating templates. Subsequent removal of the template molecule provides recognition sites in the polymer that ideally resemble the template in terms of shape, size and functionality. Rebinding of the target molecule within these pre-formed sites can occur when the polymer is incubated in the presence of the template molecule. However, removing of template after polymerization is difficult because cross-linked polymer materials tend to be insoluble. This review paper describes work on new non-covalent molecular imprinting technologies applied to fibrous materials and electrospun fibres that are suitable for selected target recognition. This method has the potential of becoming a tool for producing truly simple, rapid and robust receptors on membranes of the type in regular use in the food industry, making the in-process simultaneous removal of undesirable co-product chemicals and microbial toxins a commercial possibility.     

分子印迹固相萃取技术在食品农药残留分析中的应用

分子印迹技术是人工制备具有对特定的分子存在高选择性结合位点的高分子聚合物,分子印迹固相萃取技术由于具有高通量、高特异性,在食品痕量成分的分离、净化、富集中具有广阔的应用前景。文中综述了分子印迹固相萃取技术在检测食品中残留的三嗪类、苯基尿类、磺酰脲类及其它农药中的应用、分子印迹技术的最新进展和在应用中存在的问题等。     

花椒麻味物质分子印迹聚合物的制备及吸附特性

为实现对花椒麻味物质经济高效的纯化制备,本实验采用分子印迹技术,以甲基丙烯酸为功能单体,花椒麻味物质为模板分子,合成对花椒麻味物质具有特异性识别和吸附能力的分子印迹聚合物(molecularly imprinted polymers,MIPs),并用MIPs制成固相萃取柱用于分离纯化花椒油树脂中的花椒麻味物质。吸附动力学实验结果显示,MIPs与花椒麻味物质接触约12 h后就达到吸附平衡,对花椒麻味物质识别因子α达到3.05;等温吸附实验表明,MIPs对花椒麻味物质的吸附量高于空白聚合物,在吸附过程中模板分子花椒麻味物质与MIPs形成两种结合位点,两种结合位点的解离常数分别为1.172×10~(-2) mg/m L和3.585×10~(-2) mg/m L,对花椒麻味物质最大表观吸附量分别为11.133 mg/g和15.802 mg/g;固相萃取实验表明,该固相萃取柱可以分离出相对纯度为94.09%的花椒麻味物质。     

Application of molecularly imprinted hydrogel for the preparation of lactose‐free milk

BACKGROUND: A variety of lactose imprinted hydrogels were prepared and their binding properties were studied in comparison with blank non‐imprinted hydrogel. Methacrylamide and ethylene glycol dimethacrylate were used as functional monomer and cross‐linker, respectively. Dimethylsulfoxide was also applied as polymerisation solvent. RESULTS: Different template/monomer ratios were studied and the optimised imprinted hydrogel (MIP₂), with a lactose/methacrylamide ratio of 1:8, was selected in a rebinding test. In Scatchard analysis of MIP₂‐lactose interactions, the dissociation constant and maximum binding sites were 0.33 mmol L^?1 and 67.76 µmol g^?1 hydrogel, respectively. The selectivity of MIP₂ for lactose in aqueous media was also evaluated in comparison with different mono‐ and disaccharides. The data showed that the affinity of MIP₂ for lactose is significantly higher than other saccharides. The imprinted hydrogel was finally used as a sorbent for separation of lactose from milk. CONCLUSIONS: The results indicated that MIP₂, as an optimised imprinted hydrogel, can effectively bind lactose and decrease its concentration in milk. Copyright © 2012 Society of Chemical Industry     

分子印迹技术在分析检测领域的应用

分子印迹,属于超分子化学研究的范畴,是指以目标分子为模板,制备对该分子有特异选择性识别的聚合物的过程。分子印迹聚合物以其结构预定性、特异识别性和实用性的特点,引起了全世界范围的关注。因其具有与天然抗体同样的识别性能和与高分子同样的抗腐蚀性能的双重优点,因而广泛应用于生物工程、临床医学、环境监测、食品工业等众多领域。本文综述了分子印迹技术的发展历程,分子印迹聚合物的制备原理及方法以及在固相萃取、色谱分离、膜分离以及传感器领域的应用。色谱分离领域中对分子印迹在高效液相色谱、薄层色谱和毛细管电泳,以及传感器领域中分别对分子印迹光学传感器和电化学传感器的应用现状进行了阐述,最后对该技术进行了展望。     

Synthesis and evaluation of molecularly imprinted polymers as sorbents of moniliformin

Moniliformin is a low molecular weight mycotoxin that has worldwide potential to contaminate cereal grains. Although several traditional methods have been developed to detect moniliformin, the lack of anti-moniliformin antibodies has created a need for materials that recognize moniliformin at the molecular level through a binding mechanism. To address this issue, the authors synthesized molecularly imprinted polymers that bind moniliformin. Imprinted and non-imprinted polymers were evaluated by equilibrium binding assays and moniliformin concentrations were measured by LC analysis using ultraviolet light detection. Successful polymers were imprinted with toxin analogues as the templates; non-imprinted polymers exhibited minimal binding in acetonitrile under the assay conditions. Selected imprinted polymers also bound moniliformin in ethanol, methanol and dimethyl formamide. Significant differences in moniliformin binding by the polymers were dependent on polymer composition, and these differences were highly dependent on the template used to imprint the polymer. Polymers were further evaluated as sorbents for molecularly imprinted solid-phase extraction (MISPE), and an imprinted polymer was used for preconcentration and clean-up of a moniliformin spiked corn extract.     

Selective solid-phase extraction using molecular imprinted polymer for the analysis of diethylstilbestrol

A simple imprinted amino-functionalized silica gel material was synthesized by combining a surface molecular imprinting technique with a sol–gel process for solid-phase extraction–high performance liquid chromatography (SPE–HPLC) determination of diethylstilbestrol (DES). Activated silica gel was used as the supporter and non-imprinted silica sorbent was synthesized without the addition of DES using the same procedure as that of DES-imprinted silica sorbent. Compared with non-imprinted polymer particles, the prepared DES-imprinted silica sorbent showed high adsorption capacity, significant selectivity, good site accessibility and fast binding kinetics for DES. The maximum static adsorption capacity of the DES-imprinted and non-imprinted silica sorbent for DES was 62.58 mg g⁻¹ and 19.89 mg g⁻¹, respectively. The relatively selective factor value of this DES-imprinted silica sorbent was 61.7 at the level of 50 mg L⁻¹. And the uptake kinetics was fairly rapid so that the adsorbent equilibrium was achieved within 10 min. Furthermore, the DES-imprinted polymers were used as the sorbent in solid-phase extraction to determine DES in fish samples. The MIP–SPE–HPLC method showed higher selectivity and good recoveries higher than 87.5% (R.S.D. 11.6%).     

乙酸薄荷酯分子印迹聚合物的制备及其吸附特性

本文分别考察了不同单体、反应溶剂、充氮时间、反应温度、单体添加量、交联剂添加量对乙酸薄荷酯分子印迹聚合物制备的影响。结果表明,以乙酸薄荷酯为模板分子,丙烯酰胺为单体,以N,N-二甲基甲酰胺为反应溶剂制备的聚合物,其选择性比较好,通过聚合物的吸附分离,可以将薄荷素油中乙酸薄荷酯的含量提高到14.65%;而当单体、交联剂添加量与模板分子量的比例为1:4:16时,制备的聚合物对模板分子有较高的结合性能,结合量为5.09 mg/g,对乙酸薄荷酯和薄荷醇的分离因子为1.46,说明印迹聚合物对乙酸薄荷酯具有良好的吸附选择性。     

Solid-Phase Extraction of Florfenicol from Meat Samples by a Newly Synthesized Surface Molecularly Imprinted Sol–Gel Polymer

A new molecularly imprinted polymer (MIP) as a solid-phase sorbent for selective extraction of florfenicol (FF) was prepared by combination of the surface molecular imprinting technique with the sol–gel process. The FF-imprinted silica sorbent was prepared using FF as template, 3-aminopropyltriethoxysilane as functional monomer and tetraethoxysilicate as cross-linker on the silica gel support. The non-imprinted silica (NIP) was synthesized in the same way without addition of FF. The MIP was evaluated as a sorbent in column extraction approach for extraction of FF from aqueous solutions followed by spectrofluorometric determination. The influence of certain variables including the sample pH, the sample volume, the sample flow rate, the type of eluent, and its flow rate on the extraction efficiency of FF was assessed. The prepared FF-MIP silica sorbent showed higher adsorption capacity (64.9 mg g^?1) and significant selectivity than the corresponding NIP (11.5 mg g^?1). The FF-MIP-based solid phase extraction method was successfully applied to the separation and determination of FF from fish and chiken meat samples under the optimized extraction conditions.     

邻苯二甲酸二(2-乙基己基)酯磁性分子印迹聚合物的制备及吸附特性研究

本文报道了以3-(异丁烯酰氧)丙基三甲氧基硅烷(MPS)修饰的Fe3O4@SiO2纳米颗粒为磁性载体,邻苯二甲酸二(2-乙基己基)酯(DEHP)为模板分子,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,制备了对DEHP有特异识别性的新型磁性分子印迹聚合物(M-MIPs)。透射电镜(TEM)图表明该聚合物具有核壳结构,磁强计(VSM)测量表明该聚合物具有超顺磁性,这些特征使之在外磁场下可实现快速分离。静态平衡吸附实验和Scatchard分析结果表明,该聚合物存在两类不同的结合位点,平衡解离常数分别为0.26mmol/L和0.071mmol/L,最大表观结合量分别为28.23mg/g和13.09mg/g。选择性结合实验表明,与结构类似物相比,M-MIPs对模板分子具有优越的识别能力和选择性。该方法制备的聚合物可进一步用于食品中DEHP的分离和富集。     

Removal of estrogenic pollutants from contaminated water using molecularly imprinted polymers

A synthetic molecularly imprinted polymer (MIP) sorbent for estrogenic compounds was prepared using a noncovalent imprinting technique. MIP microspheres sized from 1 to 2 microm were synthesized in acetonitrile by using alpha-estradiol as the template, acrylamide as the functional monomer, and trimethylpropanol trimethacrylate as the cross-linker. When compared with the nonimprinted polymer (NIP), the MIP showed outstanding affinity toward alpha-estradiol in aqueous solution with a binding site capacity (B(max)) of 380 nmol mg(-1) MIP, imprinting effect of 35, and a dissociation constant (Kd) of 38 microM. The MIP exhibited significant binding affinity toward other related estrogenic compounds such as beta-estradiol, diethylstilbestrol, estriol, and estrone, suggesting that this material may be appropriate for treating a complex mixture of estrogenic pollutants. The feasibility of removing estrogenic compounds from environmental water by the MIP was demonstrated using lake water spiked with alpha-estradiol. In addition, the MIP reusability without any deterioration in performance was demonstrated for at least five repeated cycles.     

有机磷分子印迹聚合物的制备及其吸附性能评价

目的 制备出有机磷类分子印迹聚合物(molecular imprinted polymers,MIPs)并对其进行吸附性能评价.方法 选用氯代磷酸二苯酯为虚拟模板、以甲基丙烯酸(methacrylic acid,MAA)为功能单体、三羟甲基丙烷三甲基丙烯酸酯(trimethylolpropane trimethacry...