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。     

氟哌酸分子印迹共混膜的制备及结构表征

以氟哌酸为模板分子,α-甲基丙烯酸为功能单体,三甲氧基丙烷三甲基丙烯酸酯为交联剂,利用本体聚合方法制备了具有特异选择性的氟哌酸分子印迹聚合物,并利用聚砜与氟哌酸分子印迹聚合物共混的方法制备了分子印迹聚合物膜.运用红外光谱分析和透射电子显微镜研究了氟哌酸分子印迹聚合物的结构.运用扫描电子显微镜研究了分子识别膜的机理和吸附性能,运用平衡结合实验法证明了分子识别膜对氟哌酸表现出了较高的选择性.     

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.     

复合分子印迹聚合物体系选择性富集蛋白质样品中的溶菌酶

考察了功能单体与模板蛋白的反应摩尔比、溶液pH值及离子强度对功能单体与模板蛋白之间相互作用的影响, 得出制备分子印迹聚合物的最佳条件. 在最佳条件下, 以溶菌酶(Lyz)为模板分子, 丙烯酰胺(AA)和N,N’-亚甲基双丙烯酰胺(BisAA)为聚合基质, 二氧化硅为固体制孔剂, 制备了复合分子印迹聚丙烯酰胺凝胶, 并用平衡吸附实验研究了其吸附性能和识别选择性. 研究结果表明, 该聚合物对模板蛋白有较高的亲和性、选择性和吸附容量,可以从蛋白质混合溶液中分离富集模板分子.     

模拟受体聚合物的合成及吸附行为研究

采用紫外光引发聚合的分子印迹技术,分别制备阿替洛尔、美托洛尔、尼莫地平、酮糠唑4种模板化合物的分子印迹聚合物(molecularlyimprinted polymers,MIP).利用紫外平衡吸附法研究了聚合物的吸附性能和选择识别能力.结果表明,阿替洛尔、美托洛尔印迹聚合物对各自的模板分子呈现良好的再识别性能,而尼莫地平、酮糠唑印迹聚合物对原模板则几乎没有识别能力.Scatchard分析显示了功能单体甲基丙烯酸(MAA)与模板分子阿替洛尔、美托洛尔在自组装过程中通过氢键和离子键形成了至少两类不等价的结合位点.对底物交叉结合实验也表明阿替洛尔、美托洛尔这两种印迹聚合物具有良好的选择性,分离因子α值分别达到了1.75和1.62,而空白聚合物则分别仅为1.07和0.97.     

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.     

不同功能单体合成的谷胱甘肽分子印迹聚合物的研究

采用分子印迹技术, 以谷胱甘肽为模板分子, 以丙烯酰胺、甲基丙烯酸为功能单体制备分子印迹聚合物; 通过静态吸附试验, 探讨了合成分子印迹聚合物时模板分子与功能单体的物质的量比、上样液pH 值、吸附平衡时间、上样液浓度对聚合物吸附性能的影响; 实验结果表明: 以丙烯酰胺、甲基丙烯酸为功能单体制备谷胱甘肽分子印迹聚合物时,谷胱甘肽与丙烯酰胺、甲基丙烯酸的最适摩尔比分别为1:5 和1:4, 以及最适静态吸附条件为: 上样液pH 值分别为3.0 和5.0 左右; 上样液浓度分别为1.50～2.00 g/L 和1.00～1.50 g/L; 静态吸附平衡时间为18 和20 h 左右. 同时也探讨了分子印迹聚合物对谷胱甘肽结构类似物的吸附性能, 结果表明, 所合成的分子印迹聚合物对谷胱甘肽具有良好的选择性吸附能力. 同时也研究了分子印迹聚合物对酵母抽提物中谷胱甘肽的吸附性能, 以丙烯酰胺和甲基丙烯酸为功能单体制备的分子印迹聚合物对混合体系中谷胱甘肽的一次性提取率分别为41%和77%. 分子印迹聚合物均表现出了较好的吸附特性, 为分离提纯谷胱甘肽提供一种可选择的途径.     

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。     

噻吩分子印迹聚合物的合成及其识别性能研究

采用分子印迹技术合成了噻吩分子印迹聚合物。研究了聚合物的吸附性能和识别性能,并考察了影响聚合物吸附性能的因素(如:功能单体、交联剂、溶剂以及模板分子与功能单体的摩尔比等)。结果表明:以噻吩为模板分子,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,氯仿为溶剂,反应温度60℃,在偶氮二异丁腈引发下合成的噻吩分子印迹聚合物对噻吩具有较好的吸附性能和识别特性,可为石油产品进行深度脱硫提供理论依据。     

沉淀聚合法制备水杨酸分子印迹微球及其性能研究

以水杨酸(SA)为模板分子,丙烯酰胺(AM)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,利用沉淀聚合法制备了对水杨酸具有较高选择性与较高亲和性的分子印迹聚合物微球(MIPs)。用傅里叶红外光谱和环境扫描电镜表征印迹聚合物微球的结构和形貌,采用静态吸附法考察了水杨酸分子印迹聚合物微球的吸附性能。结果表明,当SA:AM:EDMA摩尔比为1:4:20时,得到的分子印迹聚合物微球粒径均一,球形度较好,对水杨酸具有较好的选择吸附性,最大表观结合量可达到52.42mg/g。     

Ultrasensitive separation of methylprednisolone acetate using a photoresponsive molecularly imprinted polymer incorporated polyester dendrimer based on magnetic nanoparticles

We developed an approach for the use of polyester dendrimer during the imprinting process to raise the number of recognized sites in the polymer matrix and improve its identification ability. Photoresponsive molecularly imprinted polymers were synthesized on modified magnetic nanoparticles involving polyester dendrimer which uses the reactivity between allyl glycidyl ether and acrylic acid for the high‐yielding assembly by surface polymerization. The photoresponsive molecularly imprinted polymers were constructed using methylprednisoloneacetate as the template, water‐soluble azobenzene involving 5‐[(4, 3‐(methacryloyloxy) phenyl) diazenyl] dihydroxy aniline as the novel functional monomer, and ethylene glycol dimethacrylate as the cross‐linker. Through the evaluation of a series of features of spectroscopic and nano‐structural, this sorbent showed excellent selective adsorption, recognition for the template, and provided a highly selective and sensitive strategy for determining the methylprednisoloneacetate in real and pharmaceutical samples. In addition, this sorbent according to good photo‐responsive features and specific affinity to methylprednisoloneacetate with high recognition ability, represented higher binding capacity, a more extensive specific area, and faster mass transfer rate than its corresponding surface molecularly imprinted polymer.     

环丙沙星分子印迹聚合物的合成及识别性能研究

采用分子印迹技术合成了以环丙沙星为印迹分子,以甲基丙烯酸和4-乙烯基吡啶同时为功能单体的分子印迹聚合物。运用平衡结合实验研究了印迹聚合物的吸附特性和选择识别能力。Scatchard分析表明,在所研究的浓度范围内,分子印迹聚合物中形成了两类不同的结合位点。底物选择实验表明,这种聚合物对环丙沙星呈现高的选择结合能力。     

沉淀聚合制备诺氟沙星-Zn2+分子印迹聚合物及其印迹方式的研究

采用沉淀聚合的方式以诺氟沙星(NFA)-Zn2+为模板分子,乙二醇二甲基丙烯酸酯为交联剂,分别选取酸性功能单体甲基丙烯酸与碱性功能单体4-乙烯基吡啶制备了诺氟沙星-Zn2+的分子印迹聚合物.通过紫外光谱研究发现诺氟沙星与Zn2+及两种功能单体均发生了金属配位印迹作用且形成了比例不同的印迹复合物.红外光谱的功能基团的表征结果显示,甲基丙烯酸与诺氟沙星-Zn2+形成了以诱导作用占优的三元配合物,而4-乙烯基吡啶则与诺氟沙星-Zn2+形成了共轭作用占优的三元配合物.扫描电镜及粒径分布实验表征了聚合物的物理特性,结果显示印迹聚合物的表面存在孔及孔道结构而非印迹聚合物的表面较致密不存在孔且制备的印迹聚合物的粒径均在100μm以下,其平均粒径为39μm.等温结合及选择性实验的结果表明4-乙烯基吡啶为功能单体制备的印迹聚合物的选择性识别性能优于甲基丙烯酸为功能单体制备的印迹聚合物,其特异性吸附容量和印迹指数分别为66.84μmol/g和4.207.同时在混合溶液的选择性实验中以4-乙烯基吡啶(4-VP)为功能单体制备的印迹聚合物的选择识别诺氟沙星的能力优于以甲基丙烯酸为功能单体的聚合物,其识别因子分别为3.408和2.909,而非印迹聚合物对底物的吸附量较小且识别因子均接近于1,说明非印迹聚合物对底物的识别为非选择性的.     

表面印迹法制备钴(Ⅱ)离子印迹硅胶及性能

采用表面印迹技术, 以Co(Ⅱ)离子作为印迹离子, 二乙烯三胺基丙基三甲氧基硅烷为功能分子, 硅胶为支撑物, 环氧氯丙烷为交联剂, 在硅胶表面制备Co(Ⅱ)离子印迹硅胶材料, 利用红外光谱仪、扫描电镜和热重分析仪等进行了表征, 采用平衡吸附法研究了印迹硅胶材料的吸附性能和选择识别能力. 结果表明, 印迹硅胶材料和非印迹硅胶材料的最大吸附量分别为35.2和6.5 mg/g; 印迹硅胶材料对Co(Ⅱ)离子的吸附行为符合Langmuir模型; 20 min即可达到吸附平衡; 当pH=3.9~7.8时, 印迹硅胶材料保持了较好的吸附容量; 印迹硅胶材料对Co(Ⅱ)离子具有较强的选择性识别能力; 重复使用时性能稳定.     

Separation and determination of estrone in environmental and drinking water using molecularly imprinted solid phase extraction coupled with HPLC

Estrone has been identified as an important potential endocrine-disrupting compound, so that sensitive and reliable analytical methods are required for its determination and the assurance of human health. Using estrone as the template, acrylamide as the functional monomer, and methacryloxypropyltrimethoxysilane as the cross-linker, an organic-inorganic hybrid material has been synthesized by the molecular imprinting technique combined with a non-hydrolytic so-gel process. The synthesized polymer was characterized by FT-IR and static adsorption experiments, and the results showed that it had good recognition and selective ability for estrone. A novel method for separation and determination of trace estrone in water samples was developed using molecularly imprinted solid phase extraction coupled with HPLC. Under the selected experimental condition, the detection limit (S/N = 3) was 9.3 ng/L, and the RSD for five replicate extractions of 10 mug/L estrone was less than 5.0%. This method was employed for quantitative determination of estrone in river, lake, and tap water with recoveries ranging from 83.38 to 98.12%.     

Development of molecularly imprinted microspheres for the fast uptake of 4‐cumylphenol from water and soil samples

Molecularly imprinted microspheres containing binding sites for the extraction of 4‐cumylphenol have been prepared for the first time. The imprinted microspheres were synthesized by a precipitation method using 4‐cumylphenol as a template molecule, methacrylic acid as a functional monomer and divinylbenzene‐80 as a cross‐linker for polymer network formation. The formation and the morphology of molecularly imprinted microspheres were well characterized using infrared spectroscopy, thermogravimetric studies, and scanning electron microscopy. The Brunauer–Emmett–Teller analysis revealed the high surface area of the sorbent indicating formation of molecularly imprinted microspheres. The developed microspheres were employed as a sorbent for the solid‐phase extraction of 4‐cumylphenol and showed fast uptake kinetics. The sorption parameters were optimized to achieve efficient sorption of the template molecule, like pH, quantity of molecularly imprinted microspheres, time required for equilibrium set‐up, sorption kinetics, and adsorption isotherm. A standard method was developed to analyze the sorbed sample quantitatively at 279 nm using high‐performance liquid chromatography with diode array detection. It was validated by determining target analyte from synthetic samples, bottled water, spiked tap water, and soil samples. The prepared material is a selective and robust sorbent with good reusability.     

双甘氨肽分子印迹聚合物微球的吸附性能研究

以双甘氨肽(Gly-Gly)为印迹分子,丙烯酰胺(AM)、二甲基丙烯酸乙二醇酯(EDMA)分别作为功能单体和交联剂,在低温条件下采用乳液聚合于水相中制备了双甘氨肽分子印迹聚合物微球(Gly-Gly-MIPMs)。通过静态、动态平衡吸附和薄层色谱(TLC)分离实验,研究了Gly-Gly-MIPMs的选择吸附性能,并进行了Scatchard模型分析。结果表明,Gly-Gly-MIPMs对Gly-Gly分子具有较好的特异性吸附,最大单位饱和吸附量0.428mmol/g,印迹因子2.19。     

咖啡因分子印迹固相萃取柱的制备及应用

以咖啡因作为模板分子,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,制备了咖啡因分子印迹聚合物(MIP)。与非印迹聚合物(NIP)相比,MIP对咖啡因具有更高的吸附容量和选择性,MIP和NIP对咖啡因的最大静态吸附量分别为28.1和16.5mg/g,相对选择因子为1.25。以咖啡因分子印迹聚合物为固相萃取填料,结合高效液相色谱(HPLC),建立了茶水中咖啡因浓度及人饮茶后血清中咖啡因浓度的检测方法。考察了洗脱剂种类和用量对咖啡因回收率的影响。当萃取柱依次以2mL水活化,水溶液上样,2mL水淋洗,6mL甲醇-乙酸(9∶1,V/V)洗脱,咖啡因在MIP固相萃取柱上的回收率达到97.5%,而在NIP柱上的回收率仅为54.9%。     

Extraction of Anthraquinones from Rhubarb by a Molecularly Imprinted–Matrix Solid-Phase Dispersion Method with HPLC Detection

A simple method based on matrix solid-phase dispersion for selective extraction of anthraquinones from rhubarb samples was developed using a molecularly imprinted polymer as sorbent. The molecularly imprinted polymer was prepared using emodin as the template molecule, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linking agent. The polymer was characterized by scanning electron microscopy and Fourier-transform infrared spectrometry. Isothermal adsorption and dynamic adsorption experiments were performed. The best extraction conditions for anthraquinones were obtained at a ratio of molecularly imprinted polymer to sample of 1:1, a dispersion time of 5 minutes, with 5% aqueous methanol as the washing solvent, and an elution solvent of methanol-acetic acid (99:1, v/v). Once the matrix solid-phase dispersion process was optimized, the extract was reacted with 8% hydrochloric acid for hydrolysis. The anthraquinones extracted from rhubarb were determined by liquid chromatography. The detection limits of chrysophanol, emodin, physcion, and aloe-emodin were 0.23, 0.24, 0.28, and 0.27 µg mL^?1, respectively. The proposed method was compared with the method in Chinese pharmacopoeia, and the results show that the extraction yield of anthraquinones obtained by molecularly imprinted polymer–matrix solid-phase dispersion method was higher. Moreover, the proposed method is faster and simpler and can achieve extraction and purification in the same system.     

Exploration of a ternary deep eutectic solvent of methyltriphenylphosphonium bromide/chalcone/formic acid for the selective recognition of rutin and quercetin in Herba Artemisiae Scopariae

Methyltriphenylphosphonium bromide/chalcone/formic acid, a green ternary deep eutectic solvent, was applied as a functional monomer and dummy template simultaneously in the synthesis of a new molecularly imprinted polymer. Ternary deep eutectic solvent based molecularly imprinted polymers are used as a solid‐phase extraction sorbent in the separation and purification of rutin and quercetin from Herba Artemisiae Scopariae combined with high‐performance liquid chromatography. Fourier transform infrared spectroscopy and field‐emission scanning electron microscopy were applied to characterize the deep eutectic solvent based molecularly imprinted polymers synthesized using different molar ratios of chalcone. The static and competitive adsorption tests were performed to examine the recognition ability of the molecularly imprinted polymers to rutin and quercetin. The ternary deep eutectic solvent consisting of formic acid/chalcone/methyltriphenylphosphonium bromide (1:0.05:0.5) had the best molecular recognition effect. After optimization of the washing solvents (methanol/water, 1:9) and eluting solvents (acetonitrile/acetic acid, 9:1), a reliable analytical method was developed for strong recognition towards rutin and quercetin in Herba Artemisiae Scopariae with satisfactory extraction recoveries (rutin: 92.48%, quercetin: 94.23%). Overall, the chalcone ternary deep eutectic solvent‐based molecularly imprinted polymer coupled with solid‐phase extraction is an effective method for the selective purification of multiple bioactive compounds in complex samples.