马拉硫磷分子印迹聚合物的制备及其在固相萃取中的应用

以马拉硫磷为模板分子,采用原位逐步聚合法制备了具有良好识别性能的分子印迹聚合物(MIPs),考察了马拉硫磷、甲基对硫磷、对硫磷及甲胺磷在马拉硫磷聚合物的选择性分离富集特性。用聚合物固相萃取了蜂蜜、蔬菜和天然水中的马拉硫磷。结果表明,聚合物对模板分子产生了印迹效应,对马拉硫磷有明显的选择性。流速为1.0 mL/min,进...     

基于N,O-双异丁烯酰乙醇胺为交联功能单体的苯磺隆分子印迹聚合物膜的制备及其性能研究

以苯磺隆为模板分子, N,O-双异丁烯酰乙醇胺为交联功能单体, 在尼龙-6膜上通过紫外光照引发合成了分子印迹聚合物膜, 并用扫描电镜对其表面形态进行了表征. 用紫外分光光谱法研究了模板分子与交联功能单体之间的相互作用. 印迹因子的测定和底物竞争渗透实验结果表明, 分子印迹聚合物膜对模板分子苯磺隆具有较高的选择性, 而非分子印迹聚合物膜没有选择性.     

制备牛血红蛋白印迹聚合物的初步研究

采用凝胶法,以丙烯酰胺为单体.N,N'-甲叉双丙烯酰胺为交联剂,制备了牛血红蛋白的分子印迹聚合物.通过考察不同单体用量对所制备的分子印迹聚合物的吸附性能的影响,得到优化制备条件.用吸附溶液的光吸收性质及电镜等对印迹聚合物的选择性吸附特性和形态特征进行表征.结果表明,制备的分子印迹聚合物对模板分子牛血红蛋白可以选择性吸附,具有很好的发展潜力.     

对羟基苯乙酮分子印迹聚合物的制备及性能研究

采用分子印迹技术,以对羟基苯乙酮为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了对模板分子对羟基苯乙酮具有良好选择性的印迹聚合物.通过静态平衡结合法以及Scatchard分析法研究了该聚合物的结合能力和选择性能.结果表明,该印迹聚合物平衡离解常数Kd=0.415 mmol/L,最大表观结合量Qmax=144.79 μmol/g.红外光谱研究表明聚合物中存在着与模板分子相互作用的特征基团.     

本体聚合法制备2-氯酚分子印迹聚合物及其性能评价

采用本体聚合法,以2-氯酚为模板分子,4-乙烯吡啶为功能单体,三羟甲基丙烷三甲基丙烯酸酯为交联剂合成了一系列分子印迹聚合物,并通过选择性实验和静态吸附实验对聚合物的选择性及吸附性能进行评价.结果显示:当以甲苯作为致孔剂,功能单体与模板分子的摩尔比为2:1时,聚合物对模板分子的印迹因子为1.71,亲和位点总数Bmax为0.1137 mmol/g,具有最优的选择性和吸附能力.     

流动注射-化学发光分子印迹技术测定敌百虫

采用分子印迹技术,以甲基丙烯酸为聚合物基体,敌百虫为模板分子,制备在空间结构和结合位点上与敌百虫匹配的分子印迹聚合物,采用扫描电镜进行形貌的表征.研究该聚合物的结合特性,测定分子印迹聚合物对敌百虫的吸附和选择识别能力,将分子印迹聚合物制备成柱,利用KMnO4、HCl化学发光体系,建立了测定敌百虫的高选择性分子印迹化学发...     

内分泌干扰物雌酮分子印迹新型吸附功能材料的制备及其选择性能研究料

采用分子印迹本体聚合法,制备了对内分泌干扰物雌酮具有高选择识别能力的分子印迹聚合物。吸附动力学和选择性实验结果表明,与非印迹聚合物相比,印迹聚合物具有较高的吸附容量和吸附速率,对模板分子具有较高的选择性。聚合反应条件对印迹聚合物的吸附和识别性能有重要影响,以丙烯酰胺为功能单体,模板分子、功能单体和交联剂摩尔比为1：3：6,制备的印迹聚合物具有较高的选择和吸附性能。     

溶胶-凝胶法制备的罗丹明B/二氧化钛分子印迹聚合物的结构与吸附性能

以罗丹明B为模板分子,以钛酸丁酯为交联剂,采用溶胶-凝胶法在酸性条件下制备了罗丹明B二氧化钛溶胶-凝胶分子印迹聚合物;利用傅立叶变换红外光谱和透射电镜分析了分子印迹聚合物的结构,使用热重分析测定了其热稳定性,采用静态吸附和动态吸附方法考察了其吸附性能,并与非印迹聚合物进行了对比.结果表明,与非印迹聚合物相比,印迹聚合物具有网络状多孔隙凝胶微结构及对模板分子的特异性识别结合位点,因而对模板分子具有更好的吸附性能和特异选择性.其原因可能在于,模板分子上的羰基与钛酸丁酯水解产生的羟基产生氢键作用,使钛酸围绕于模板分子周围,并通过缩聚形成凝胶;当模板分子洗脱后,孔隙得到保留并形成网络状凝胶,从而能够吸附更多的模板分子.     

内分泌干扰物雌酮分子印迹新型吸附功能材料的制备及其选择性能研究

采用分子印迹本体聚合法,制备了对内分泌干扰物雌酮具有高选择识别能力的分子印迹聚合物。吸附动力学和选择性实验结果表明,与非印迹聚合物相比,印迹聚合物具有较高的吸附容量和吸附速率,对模板分子具有较高的选择性。聚合反应条件对印迹聚合物的吸附和识别性能有重要影响,以丙烯酰胺为功能单体,模板分子、功能单体和交联剂摩尔比为1:3:6,制备的印迹聚合物具有较高的选择和吸附性能。     

农药丙溴磷分子印迹聚合物微球的制备与结合性能研究

采用分子印迹技术,以丙溴磷为模板分子,分别以α-甲基丙烯酸和丙烯酰胺为功能单体,在乙腈溶液中合成了2种对丙溴磷具有选择性结合能力的分子印迹聚合物.紫外光度法研究表明,模板分子丙溴磷与α-甲基丙烯酸之间的作用强于其与丙烯酰胺之间的作用;扫描电镜的研究则表明以α-甲基丙烯酸为功能单体合成的分子印迹聚合物呈微球形,粒径约为0.5 ～2 μm;利用平衡结合实验研究了不同功能单体制备的聚合物对模板分子的结合能力及其对底物的选择性,经Scatchard模型分析,求出了聚合物的最大表观结合量(Qmax)和平衡离解常数(Kd)分别为49.44 μmol/g 和1.05 mmol/L.研究表明以α-甲基丙烯酸为功能单体合成的分子印迹聚合物对丙溴磷表现出更强的结合能力和更高的选择性.     

对硫磷分子印迹聚合物制备及其在水质检测中的应用

为了有效的分离富集水样中有机磷农药,以对硫磷为模板、三羟甲基丙烷三丙烯酸酯为交联剂,采用紫外聚合方法制备了对硫磷分子印迹聚合物(MIP)。利用紫外光谱、红外光谱研究了对硫磷与不同功能单体间作用力及印迹聚合物的结合位点。利用该MIP,建立MIP-固相萃取-气相色谱法测定水中痕量对硫磷,方法的检出限(3S/N)为0.48μg/L,加标回收率为86.2%～115.7%,相对标准偏差(n=6)为3.0%～6.6%。     

High Selective Parathion Voltammetric Sensor Development by Using an Acrylic Based Molecularly Imprinted Polymer‐Carbon Paste Electrode

The design and construction of an extra high selective voltammetric sensor for parathion by using a molecularly imprinted polymer (MIP) as recognition element was introduced. A parathion selective MIP and a nonimprinted polymer (NIP) were synthesized and then incorporated in the carbon paste electrode. The MIP‐CP electrode showed very high recognition ability in comparison to NIP‐CP. It was shown that electrode washing after parathion extraction, led to enhanced selectivity. Some parameters affecting the sensor response were optimized and then the calibration curve was plotted. A dynamic linear range of 1.7–900 nM was obtained. The detection limit of the sensor was calculated as 0.5 nM. This sensor was used successfully for parathion determination in real samples such as ground water and vegetables.     

Development of a competitive format sorbent assay for the determination of parathion in water using molecular imprinted polymer as specific sorbent carrier

<正>A rapid,simple,and reliable competitive molecular imprinted polymer sorbent assay(MIPSA) was developed and validated for measurement of parathion in water samples.This assay employed a molecular imprinted polymer(MIP) that was synthesized with non-covalent imprinting method as capture reagent and p-aminoparathion conjugate of horseradish peroxidase(para-HRP) as an enzyme label.The assay depended on a competitive binding reaction between the enzyme conjugate and analyte for the binding sites of the MIP.The optimized analysis conditions of 10 ng mL~(-1) para-HRP and 10 mg mL~(-1) polymer were found.The assay was acceptable to detect parathion in water samples under the optimized conditions,with a limit of detection of 50 ng mL~(-1).Mean analytical recoveries of added parathion in water samples ranged from 101.2%to 105%.The precision of the assay was satisfactory; relative standard deviation ranged from 4.3%to 6%.     

Determination of Parathion‐methyl in Vegetables by Fluorescent‐Labeled Molecular Imprinted Polymer

A novel sensor for the determination of parathion‐methyl based on couple grafting of functional molecular imprinted polymers (MIPs) was fabricated which is developed by anchoring the MIP layer on surfaces of silica particles embedded CdSe quantum dots by surface imprinting technology. The synthesized molecular imprinted silica nanospheres (CdSe@SiO₂@MIP) allow a high selectivity and sensitivity of parathion‐methyl via fluorescence intensity decreasing when the MIP material rebinding the parathion‐methyl molecule. Compared with the MIP fabricated in traditional method, the template of parathion‐methyl was easier to remove from the CdSe@SiO₂@MIP imprinted material. Under optimal conditions, the fluorescence intensity of parathion‐methyl at the imprinted sensor was detected by spectrofluorophotometer. The relative fluorescence intensity of CdSe@SiO₂@MIP decreased linearly with the increasing concentration of parathion‐methyl ranging from 0.013 mg·kg⁻¹ to 2.63 mg·kg⁻¹ with a detection limit (3δ) of 0.004 mg·kg⁻¹ (S/N=3), which is lower than the MIP in tradition. The imprinted film sensor was applied to detect parathion‐methyl in vegetable samples without the interference of other organophosphate pesticides and showed a prosperous application in the field of food safety.     

甲醛分子印迹聚合物的制备、性能及水产品测定

以甲醛为模板分子,α-甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,用氯仿做溶剂,制备了甲醛分子印迹聚合物,并优化了此制备方法,在模板分子、功能单体和交联剂的摩尔比为1:2:20,预聚合时间为4 h,聚合时间为8 h的条件下制备的聚合物对甲醛的特异性吸附能力最好,当甲醛溶液的浓度为2 mmol/L时聚合物对甲醛的吸附量达到了12.40×10^-2 mmol/g。 对市售鱿鱼处理后用高效液相色谱法测定得样品中甲醛的浓度是5.92 mg/Kg,将该样稀释100倍以后甲醛已无法检出,经MIP柱富集后检测计算样品中甲醛浓度为5.76 mg/Kg,表明该聚合物用于样品前处理高效且结果无显著性差异。     

羟丙哌嗪分子印迹的固相萃取

以L-羟丙哌嗪为模板分子, α-甲基丙烯酸为功能单体, 三羟甲基丙烷三甲基丙烯酸酯为交联剂, 合成了羟丙哌嗪分子印迹聚合物, 利用该聚合物进行羟丙哌嗪固相萃取应用研究. 实验证明, 所合成的分子印迹聚合物具有良好的识别萃取模板分子羟丙哌嗪的能力, 能够用于羟丙哌嗪的富集浓缩, 而空白聚合物却不具备这样的特性. 考察了模板分子与其结构类似物苄基哌嗪、N-异丙基哌嗪和乙氧基羰基哌嗪的固相萃取分离情况, 研究表明, 虽然其中的苄基哌嗪在印迹材料上具有最强的保留, 但是通过先后使用不同的洗脱溶液实现了模板分子与苄基哌嗪的选择性分离.探讨了印迹识别机理,并用PM3 半经验计算机模拟方法进行了辅助分析验证.     

Separation of Epigallocatechin Gallate from Natural Plant Extracts Using Crowding Agents—Assisted Imprinted Polymers

A methodology-based molecularly imprinted polymer (MIP) was proposed to separate epigallocatechin gallate (EGCG) from natural plant extracts. A molecular crowding agent was introduced to improve the affinity and recognizing ability of EGCG in the preparation of an MIP monolith. Acrylamide was used as the functional monomer, and ethylene glycol dimethacrylate was the crosslinking monomer, using a solution of polystyrene in tetrahydrofuran as a molecular crowding agent with isooctane as a coporogen. In addition, it was found that the ratio of the macromolecule agent, the amount of templates and crosslinking degree, and the composition of the mobile phase greatly affected the retention of the template and performance of molecular recognition. The imprinting factor of the resulting MIP monolith obtained was up to 9.67. The resulting MIP can be used to purify EGCG from crude tea polyphenol efficiently with mean recoveries of 87.42 %.

     

Molecularly imprinted polymer with high-fidelity binding sites for the selective extraction of barbiturates from human urine

In this paper we describe the synthesis of a molecularly imprinted polymer (MIP) by precipitation polymerisation, with barbital as the template molecule, and the application of the barbital MIP as a molecularly selective sorbent in the solid-phase extraction (SPE) of barbiturates from human urine samples. The MIP was synthesised by precipitation polymerisation using 2,6-bis-acrylamidopyridine as the functional monomer and DVB-80 as the cross-linking agent. The spherical MIP particles produced were 4.2 ± 0.4 μm in diameter; a non-imprinted control polymer (NIP) in bead form was 4.8 ± 0.4 μm (mean±standard deviation) in diameter. The particles were packed into a solid-phase extraction cartridge and employed as a novel sorbent in a molecularly imprinted solid-phase extraction (MISPE) protocol. The MIP showed high selectivity for the template molecule, barbital, a feature which can be ascribed to the high-fidelity binding sites present in the MIP which arose from the use of 2,6-bis-acrylamidopyridine as the functional monomer. However, the MIP also displayed useful cross-selectivity for other barbiturates besides barbital. For real samples, the MIP was applied for the extraction of four barbiturates from human urine. However, due to the high urea concentration in this sample which interfere the proper interaction of barbiturates onto the MIP, a tandem system using a commercially available sorbent was developed.     

Syntheses of steroid-based molecularly imprinted polymers and their molecular recognition study with spectrometric detection

Recognition of five steroid compounds, beta-estradiol, ethynylestradiol, estradiolbenzoate, testosterone and methyltestosterone were studied using a synthesized molecularly imprinted polymer (MIP). When beta-estradiol was used as the template molecule, the polymer was synthesized with methacrylic acid (MAA) as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as the cross linking agent through non-covalent interactions. It is found that the kind of porogen solvent and the polymerization conditions greatly affected the binding ability of a MIP to a certain molecule. Releasing of the template was performed by continuous extraction with methanol containing 10% acetic acid in a Soxhlet extractor. Our results indicated that such carefully synthesized MIP showed specific affinity toward beta-estradiol in the adsorption process.     

硅胶表面水胺硫磷分子印迹聚合物的制备及其性能

以水胺硫磷为模板分子,甲基丙烯酸（MAA）为功能单体,三羟甲基丙烷三甲基丙烯酸酯（TRIM）为交联剂,采用表面分子印迹技术,以商品化硅胶为基体,合成了对有机磷农药水胺硫磷具有良好选择性的表面分子印迹聚合物（MIP）。 用红外光谱（IR）、扫描电子显微镜（SEM）和元素分析等技术分别对表面印迹聚合物进行了结构表征和表面形态观察;静态吸附平衡实验和Scatchard分析表明,该印迹聚合物中存在着两类不同的结合位点,离解常数分别为4.84×10-3和15.2×10-3 mol/L。与非印迹聚合物相比,MIP对水胺硫磷有较大的特异性吸附能力,其印迹因子为2.73。