左氧氟沙星印迹聚合物微球及其特异吸附研究

以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法制备了左氧氟沙星印迹聚合物(MIP)微球,用SEM和IR分别对微球形貌和结构进行表征,用静态吸附法和Scatchard分析考察了聚合物微球对模板及其结构类似物的吸附行为和选择性识别能力.结果表明,MIP对模板分子的吸附平衡速度快,40min即可达到吸附...     

TNT分子印迹聚合物微球的合成与性能研究

以三硝基甲苯(TNT)为模板分子,EDMA为交联剂,采用沉淀聚合法制备了TNT分子印迹微球.讨论了溶剂用量、模板分子用量、功能单体种类等对分子印迹微球的形貌及吸附性能的影响;利用紫外吸收光谱和BET表征了印迹聚合物微球的结合位点相互作用与印迹孔穴结构;通过平衡吸附和选择性吸附实验,研究了印迹聚合物微球的吸附性能和选择性识别性能.结果表明,以丙烯酰胺为功能单体制备的分子印迹聚合物为规则的球形,内部含有分子印迹孔穴,微球的粒径为1～2μm.印迹聚合物微球可在30 min内达到吸附平衡,在1 mmol/L的TNT乙醇溶液中,印迹聚合物微球的平衡吸附量为32.5 mmol/kg,对TNT分离系数为25.19,具有较好的特异性吸附能力,并可选择性识别TNT分子.     

硅胶表面亮菌甲素分子印迹聚合物的制备及其性能研究

采用光接枝印迹方法,在硅胶微球表面制备了以亮菌甲素为模板分子、2-乙烯基吡啶为功能单体的分子印迹聚合物,采用荧光法优选了功能单体及比例,进一步用荧光法对印迹聚合物的吸附特性和印迹效率进行评价.结果表明.该印迹聚合物对模板分子具有特异吸附性能,印迹效率为48.6%.     

氧化还原引发制备乙氧酰胺苯甲酯分子印迹微球及其表征

以乙氧酰胺苯甲酯为模板分子,甲基丙烯酸为功能单体,季戊四醇三丙烯酸酯为交联剂,在过氧化苯甲酰和N,N-二甲基苯胺的引发作用下,制备了乙氧酰胺苯甲酯的分子印迹聚合物微球。优化的致孔溶剂为乙腈,模板、单体和交联剂的摩尔比为1∶6∶20。采用高效液相色谱法测定模板分子及其结构类似物的浓度,结合静态平衡吸附实验、吸附动力学实验和选择性评价,对聚合物的吸附性能进行了研究,所得微球的静态吸附量为15.0μmol·g-1,印迹因子为4.93。采用扫描电子显微镜、红外光谱仪和差示扫描量热仪表征聚合物的理化特性,结果表明,微球的形貌规则,印迹效应显著,热稳定性较好。本研究所采用的氧化还原引发方法具有制备简便、成本低以及特异性好等优点,为分子印迹聚合物的引发制备提供了新思路。     

壬基酚表面印迹聚合物微球的合成及分子识别特性

采用表面分子印迹技术,在二氧化硅微粒表面通过乙烯基三甲氧基硅烷接枝,以壬基酚(NP)为模板、α-甲基丙烯酸为功能单体制备了壬基酚印迹聚合物。扫描电镜及比表面分析仪测试结果表明制备的印迹聚合物呈均匀分散的微球,具有较大的比表面积。采用红外光谱表征印迹聚合物微球制备过程中的化学结构变化情况,并用平衡吸附法研究了聚合物对NP的结合性能与分子识别特性。研究结果表明,聚合物对壬基酚具有良好的结合亲和性,最大结合量可达184.6 mg/g。印迹聚合物对NP的吸附量高于其结构类似物对特辛基酚和双酚A的吸附量,表现出较高的选择性识别能力。     

种子溶胀悬浮聚合法制备香草醛分子印迹聚合物微球

以分散聚合法制备的聚苯乙烯微球为种子,采用单步溶胀悬浮聚合法,香草醛为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,在水相中成功制备了分子印迹聚合物微球,通过扫描电镜、静态吸附和高效液相色谱手段对其进行表征。结果表明,该微球对香草醛具有较高的吸附能力和良好的特异选择性,用于液相色谱固定相可将其与结构类似物阿魏酸快速基线分离。     

S-布洛芬印迹聚合物微球的制备及应用

以S-布洛芬为模板,丙烯酰胺（AM）为功能单体,二乙烯基苯（DVB）为交联剂,在甲苯-乙腈的混合溶剂中,采用沉淀聚合法制得粒径为3~6μm的印迹聚合物微球。将印迹聚合物微球用作高效液相色谱（HPLC）固定相,以乙腈为流动相,通过拆分外消旋布洛芬及分离其类似物,评价分子印迹聚合物的特异识别性能;研究了流动相中乙酸含量、流速对拆分能力的影响;通过测定分离过程中焓变、熵变及自由能的变化,对分子印迹聚合物的分离过程做了详细的解释。     

沉淀聚合法制备右旋邻氯扁桃酸分子印迹聚合物微球

以右旋邻氯扁桃酸为模板,丙烯酰胺、乙二醇二甲基丙烯酸酯分别为功能单体和交联剂,采用沉淀聚合法制备了分子印迹聚合物微球,讨论了反应介质用量、聚合温度、引发剂的种类和用量对印迹微球的影响。实验表明：分子印迹微球与传统本体聚合法制备的聚合物相比具有更高的特异识别能力,通过Scatchard分析研究了聚合物的选择结合性能,结果表明分子印迹聚合物微球在识别右旋邻氯扁桃酸分子的过程中存枉两类结合位点,而空白聚合物微球只存在一类结合位点。     

绿原酸印迹均匀微球的制备及其色谱行为研究

以绿原酸为模板,甲基丙烯酸为功能单体,二乙烯基苯为交联剂,采用沉淀聚合法制备了绿原酸印迹均匀微球。探讨了模板及功能单体类型和用量对聚合物颗粒均匀性的影响,考察了流动相组成及柱温对分子印迹柱色谱保留和选择性的影响。绿原酸均匀印迹微球的制备条件为：模板-功能单体-交联剂的用量比为0.375:1.5:7.0,摇瓶转速为15r/min时,微球直径约2.5μm,聚合物收率为35.4%。流动相组成及含水量对印迹聚合物的保留行为影响较大,当用乙腈-水混合物为流动相时,含水量增加,各化合物在印迹色谱柱上的容量因子降低：当流动相含水量高于2.5%,分子印迹聚合物失去选择识别能力;但以0.002mol L_-1磷酸缓冲液(pH3.0)-乙腈混合液为流动相时,分子印迹柱对模板的容量因子、选择性及色谱峰形都有较大改进。当二者体积比为19:1,容量因子高达90.69,其选择性相对于没食子酸和原儿茶酸高达23.10和6.562。温度影响分子印迹聚合物的选择保留能力,当温度从25℃提高到45℃时,印迹聚合物对模板的容量因子从3.52降低到2.41,选择因子降低约30%。     

绿原酸印迹微球的制备及其色谱行为研究

以绿原酸为模板,甲基丙烯酸为功能单体,二乙烯苯为交联剂,采用沉淀聚合法制备了绿原酸印迹微球。探讨了模板及功能单体类型和用量对聚合物颗粒均匀性的影响,考察了流动相组成及柱温对分子印迹柱色谱保留和选择性的影响。绿原酸印迹微球的制备条件为:模板-功能单体-交联剂的用量比为0.375∶1.5∶7.0,摇瓶转速为15r/min时,微球直径约2.5μm,聚合物收率为35.4%。流动相组成及含水量对印迹聚合物的保留行为影响较大,当用乙腈-水混合物为流动相时,含水量增加,各化合物在印迹色谱柱上的保留因子降低:当流动相含水量高于2.5%,分子印迹聚合物失去选择识别能力;但以0.002mol/L磷酸缓冲液(p H3.0)-乙腈混合液为流动相时,分子印迹柱对模板的保留因子、选择性及色谱峰形都有较大改进。当二者体积比为19∶1,保留因子高达90.69,其选择性相对于没食子酸和原儿茶酸高达23.10和6.562。温度影响分子印迹聚合物的选择保留能力,当温度从25℃提高到45℃时,印迹聚合物对模板的保留因子从3.52降低到2.41,选择性因子降低约30%。     

A novel molecular imprinting polymer for the selective adsorption of D-arabinitol from spiked urine

In this research, molecular imprinting polymers (MIPs) for D-arabinitol were synthesized using a bulk polymerization method through a noncovalent approach. The MIPs were prepared by using D-arabinitol as a template, acrylamide as a functional monomer, ethylene glycol dimethacrylateas cross-linker, benzoyl peroxide as an initiator and dimethyl sulfoxideas a porogen. MIPS was synthesized in several formulas with a different molar ratio of template to functional monomers and cross-linker. Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) were used to characterize the MIPs produced. A batch rebinding assay was used to test the binding efficiency of each formula. Batch rebinding test results revealed that MIPsF3 with a molar ratio of the template: monomer and crosslinker ratio respectively (1: 4: 25) had the highest binding capacity at 1.56 mgg ^-1 . The results of isotherm adsorption showed that the MIPs produced followed the Freundlich equation with an R-value of 0.97. The MIPs produced was also selective toward its isomeric compounds (i.e. L-arabinitol, adonitol, xylitol, and glucose). The extraction efficiency of the MIPs against D-arabinitol was 88.98%.     

基于离子液体辅助氯霉素分子印迹聚合物的制备及应用

以氯霉素(CAP)为模板,2-乙烯基吡啶(2-Vp)为功能单体,四氢呋喃和离子液体1-丁基-3-甲基咪唑四氟硼酸盐[BMIm]BF4的混合溶液为反应溶剂,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,合成了氯霉素的分子印迹及非印迹聚合物。优化功能单体、不同溶剂对印迹聚合物吸附性能的影响,结果表明,以2-乙烯基吡啶为功能单体,四氢呋喃和离子液体[BMIm]BF4(体积比1∶1)作为反应溶剂合成的分子印迹聚合物对氯霉素具有高的吸附容量,良好的特异性识别性能。氯霉素分子印迹聚合物的印迹因子为2.6,进行吸附-解吸附循环5次后,氯霉素印迹聚合物的性能稳定,可重复使用。将制备的氯霉素分子印迹聚合物作为富集材料,应用于鸡蛋样品中氯霉素的检测,回收率可达62.3%~81.1%,准确性好。     

Improving the strategy and performance of molecularly imprinted polymers using cross-linking functional monomers

A new strategy for monomer design has been investigated that combines interactive monomer functionality with a cross-linking format, giving as a result noncovalent molecularly imprinted polymers (MIPs) with improved performance. This strategy was explored under the premise that more functionality could be introduced without suffering performance losses due to reduced cross-linking. While this proved to be correct, equally important contributions to selectivity enhancement at the molecular level by conformation control and diastereomeric complexation were also discovered. Monomers derived from l-serine and l-aspartic acid were synthesized and used to prepare MIPs, with the best performance obtained for the MIP formulated with the serine-based cross-linker (N,O-bis-methacryloyl l-serine, 3), versus the aspartic-acid-based cross-linkers and the traditional methacrylic acid/ethylene glycol dimethacrylate (MAA/EGDMA) formulation. Quantitative structure-selectivity relationship (QSSR) studies revealed that the improved performance of 3 was due to three key factors: (1) the cross-linking nature of this monomer; (2) control of conformational flexibility; (3) a strong influence of monomer chirality on enantioselectivity in MIPs.     

Preparation of hydrophilic molecularly imprinted polymers for tetracycline antibiotics recognition

Hydrophilic molecularly imprinted polymers(MIPs) were prepared using tetracycline as template,methacrylic acid as monomer and glycidilmethacrylate as pro-hydrophilic co-monomer.Compared with common MIPs,the imprinting effect and adsorption amounts of hydrophilic MIPs for tetracycline(TC) were greatly improved in water media.Furthermore,the electrochemical sensor fabricated by modifying hydrophilic MIPs on glassy carbon electrode was developed for the determination of TC in foodstuff samples.     

Molecularly imprinted solid-phase extraction of matrine from radix Sophorae tonkinensis

In the study, molecularly imprinted polymers (MIPs) with special molecular recognition properties of matrine (MAT) were prepared in our lab, using melamine-urea-formaldehyde (MUF) as the functional monomer and matrine as the template. An equilibrium binding experiment was performed to investigate the binding ability of the MIPs, and indicated that the MIPs had a high adsorption and good elution ability to the target molecule MAT, when the template/functional monomer ratio (T/M) was 5 mg g(-1). Scatchard analysis and isothermal equilibrium adsorption indicated that only one kind of binding site had existed in the MAT-imprinted polymers with its dissociation constants estimated to be 3.31 × 10(-4) mol L(-1) (200-400 mesh (inch(-1))) and 6.83 × 10(-4) mol L(-1) (over 400 mesh (inch(-1))) depending on the mesh of the MIPs. MAT purification and elution experiments were carried out using MIPs as the solid-phase extraction (MISPE) sorbent, and acetone, water, and chloroform as the elution solvents. The results demonstrated that MIPs achieved their highest adsorption capability after treatment with alkaline solution, while acetone was the most efficient elution solvent. Then, a crude extraction of matrine in radix Sophorae tonkinensis was performed using these MIPs as the separation medium. The results showed that MIPs had a high MAT selectivity, and the amount of matrine content obtained by MISPE was 1.4-fold to that obtained by liquid-liquid extraction.     

吲哚美辛纳米胶体金分子印迹聚合物的制备及其在固相萃取中的应用

以吲哚美辛(IDM)为模板分子,丙烯酰胺(AA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,本体聚合法制备过程中加入纳米胶体金,合成了吲哚美辛胶体金分子印迹聚合物(MIPs/Au),利用MIPs/Au表面胶体金对蛋白吸附作用,将抗吲哚美辛的多克隆抗体固定在MIPs/Au上,得到表面固定有抗体的新型聚合物(MIPs/Au-Ab)并对其进行了表征。制备了填充材料为MIPs/Au-Ab的固相萃取柱并对其上样、淋洗和洗脱条件进行了优化,并将所制备的新型萃取柱用于水样中IDM的分离富集。抗吲哚美辛抗体交联在聚合物表面,不仅增加了萃取柱的特异性吸附容量,而且有效地降低了MIP的非特异性吸附。     

石杉碱甲分子印迹聚合物的制备、表征及其吸附性能

以硅胶为牺牲载体,石杉碱甲为模板分子,甲基丙烯酸为功能单体,二乙烯基苯为交联剂,偶氮二异丁腈为引发剂,首次制备了石杉碱甲分子印迹聚合物,并用红外光谱、扫描电子显微镜和热重分析研究了印迹聚合物的结构特征,用静态吸附法和Scatchard分析法研究了印迹聚合物的识别效能和表面位点分布特征。 结果表明,石杉碱甲印迹聚合物对模板分子具有较好的选择吸附性能,选择系数为1.399。Scatchard分析表明,印迹聚合物基体中主要存有两类吸附位点,对高亲和位点：平衡离解常数Kd1=0.776 g/L,最大表观结合量Qmax1=0.213 mg/g;对低亲和位点：平衡离解常数Kd2=0.169 g/L,最大表观结合量Qmax2=0.832 mg/g。 当该聚合物用于微固相萃取蛇足石杉粗提液中的石杉碱甲时,石杉碱甲回收率为93.5%,显示了较好的富集效果。     

三唑酮分子印迹预组装体系的分子模拟与吸附性能

以三唑酮为模板分子, 以丙烯酰胺(AM)、 丙烯酸(AA)、 甲基丙烯酸(MAA)和三氟甲基丙烯酸(TFMAA)为功能单体预组装了分子印迹聚合物体系, 采用半经验法和从头算法, 利用Hyperchem软件模拟了三唑酮与4种功能单体所组成的分子印迹预组装体系的构型、 能量、 反应配比及复合反应的结合能, 选择复合物结合能最高的功能单体用于分子印迹聚合物的合成. 采用密度泛函方法计算了模板与单体在不同致孔剂中的溶剂化能. 结果表明, 三唑酮与三氟甲基丙烯酸所形成复合物的作用力最强, 在非极性溶剂中溶剂化能最弱. 由预组装体系的差示紫外光谱法研究发现, 一分子三唑酮可与两分子三氟甲基丙烯酸在氯仿中形成氢键复合物, 与分子模拟的结果一致. 在最佳模拟条件下, 合成了三唑酮的印迹聚合物, 利用吸附等温线Langmuir和Freundlich模型研究了印迹聚合物的吸附行为及识别机理. 上述方法对于分子印迹体系的筛选及分子印迹聚合物性能的预测有重要的意义.     

STUDY ON THE NON-COVALENT INTERACTION OF APIGENIN MOLECULARLY IMPRINTED POLYMERS BY SPECTROMETRY

The non-covalent interaction between aPigenin （API） and different functional monomers （α-methylacrylic acid （MAA）, acrylamide （AM）, 2-vinylpyridine （2-Vpy） and combined functional monomers （AM/2-Vpy）） was determined by UV spectrometry, and a series of apigenin molecularly imprinted polymers （API-MIPs） was synthesized with different functional monomers through molecular imprinting technology. The relationship between the non-covalent interaction of template/functional monomer and absorption of MIPs also was studied. The results showed that the order of the strength of the non-covalent interaction between API and different functional monomers in tetrahydrofuran （THF） is as follows： 2-Vpy〉 AM/2-Vpy〉AM〉MAA, which is positive correlation to the absorption capability of corresponding MIPs, and 2-Vpy is the optimum functional monomer among the used monomer for preparing API- MIPs.     

Novel surface modified molecularly imprinted polymer focused on the removal of interference in environmental water samples for chromatographic determination

Uniformly sized molecularly imprinted polymers (MIPs) for bisphenol A (BPA) with surface modification and immobilized intervals of functional monomers afforded by utilizing 4,4'-methylenebisphenol as a pseudo component have been prepared. MIPs for BPA were prepared using 4-vinyl pyridine immobilized in the most effective interval and ethylene glycol dimethacrylate as a functional monomer and cross-linking agent, respectively. Prepared MIPs showed significant selectivity for BPA retention and removal performance for interference in actual samples as the HPLC stationary phase compared to those of ordinary MIPs. These MIPs were employed as pretreatment media of column switching HPLC and the HPLC system provided a detection limit of 0.36 ppt when electrochemical detection was used. Actual samples, including Suwannee River natural organic matter (NOM), were applied and BPA was detected in the NOM even if widely used UV detection was employed.