醚菌酯分子印迹聚合物的制备及表征

[方法]以醚菌酯为模板分子、甲基丙烯酸(MAA)为功能单体、乙二醇二甲基丙烯酸酯(EDMA)为交联剂、偶氮二异丁腈(AIBN)为引发剂,用沉淀聚合法制备了醚菌酯分子印迹聚合物。[结果]红外光谱分析表明模板分子已洗脱完全。平衡吸附实验及Scatchard分析可知MIPs最大表观结合量为97.11 mg/g。用固相萃取实验富集分离土壤中的醚菌酯,与Florisil柱相比,分子印迹固相萃取柱净化更彻底,减少了杂质对分析的干扰。[结论]沉淀聚合法制备的MIP吸附性较好,具有一定的应用价值。     

双模板分子印迹聚合物在奶粉检验中的应用研究

采用本体聚合法制备三聚氰胺(MEL)与双氰胺(DCD)双模板分子印迹聚合物(MEL/DCD-MIPs),将其作为固相萃取介质,实现了奶粉中MEL与DCD富集与纯化,建立了奶粉中两种物质同时检测的方法。通过热力学、选择性和动态结合试验表明,与单模板分子印迹聚合物相比,双模板分子印迹聚合物由于双模板-功能单体分子间的多位点协同作用而有更好的印迹效应,对MEL和DCD结合能力高于结构类似物三聚氰酸(CYA)。固相萃取试验显示,MEL/DCD-MIPs可以从市售奶粉中选择性地分离、富集MEL与DCD,对MEL与DCD的加样回收率分别为93.1%~100.1%和75.7%~82.5%,RSD均小于5.2%。所制得的MEL/DCD-MIPs可应用于奶粉等食品中氰胺类物质的检测。     

格列美脲分子印迹聚合物应用于固相萃取的研究

以降血糖药物格列美脲为模板分子,ɑ-甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用本体聚合法制备了格列美脲分子印迹聚合物(MIP),用于血浆样品前处理,建立了对加标兔血浆中格列美脲含量的固相萃取检测方法,通过高效液相色谱法测定,分子印迹固相萃取柱的回收率可达80%以上,有效地减少了基体中蛋白质等杂质对目标物检测的干扰,适用于生物样品中模板分子的富集和纯化。     

奎宁印迹聚合物的吸附与识别特性的研究

以奎宁为模板分子 ,利用分子印迹技术合成了一种新型的类似于人工受体的印迹聚合物 ,研究了它对奎宁和其它底物的吸附特性和选择性识别能力 ,并对其固相萃取性能做了初步的研究。     

烯酰吗啉分子印迹聚合物的合成及固相萃取研究

以烯酰吗啉为名义模板,甲基丙烯酸(MAA)为功能单体,二甲基丙烯酸乙二醇酯(EDMA)为交联剂,在制孔剂三氯甲烷中制备了烯酰吗啉的分子印迹聚合物。优化的模板、MAA及EDMA间的配比为1∶4∶20。采用本体聚合和悬浮聚合两种聚合方法进行MIP的制备,探讨两种聚合方法的不同及优缺点。研究还以分子印迹聚合物作为固相萃取的填料,制备固相萃取柱,对其应用性能进行评价。     

分子印迹技术在固相萃取中的应用

分子印迹技术是制备具有分子特异识别功能聚合物的一种技术。分子印迹固相萃取技术由于具有高通量和高特异性,在食品、环境、药物、生物样品中分析物的分离、净化、富集中具有广阔的应用前景。文章中综述了分子印迹固相萃取技术的应用、分子印迹技术的最新进展和在应用中存在的问题等。     

离子印迹聚合物研究进展

回顾了离子印迹聚合物方面的主要研究内容和成果。由于离子印迹聚合物具有预定识别性,制备简单、价格低廉、稳定性好,对模板离子表现出较高的选择性和亲和性,在离子分离、富集以及传感识别等领域有着广泛的应用前景。介绍了离子印迹技术的原理,并依据模板离子种类的不同（主族金属离子、过渡金属离子、稀土金属离子、锕系金属离子、阴离子等）,对各离子印迹聚合物的制备方法、吸附特性和应用性能进行了综述,并展望了离子印迹聚合物的发展方向。     

戊唑醇-三唑酮双模板分子印迹聚合物在烟叶农残检测中的应用

以戊唑醇（TBZ）和三唑酮（TDF）为双模板分子,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,按摩尔比为1∶4∶20制备了戊唑醇-三唑酮双模板分子印迹聚合物（MIPs）。考察了MIPs的吸附动力学、静态吸附及亲和位点特征和选择识别性能。结果表明,MIPs可在2.5h内达到吸附平衡,Scatchard分析得出MIPs存在高低两类亲和位点,且具有良好的组选择性和特异选择性。以MIPs作为固相萃取填料,制备分子印迹固相萃取柱（MISPE）用于烟叶样品前处理,并建立MISPE-超高效液相色谱-串联质谱法检测烟叶中（戊唑醇、三唑酮、腈菌唑和三唑醇）残留的方法。结果显示,MISPE柱对戊唑醇、三唑酮、腈菌唑和三唑醇的富集效果较好,平均回收率为72%～110.3%,相对标准偏差在2.38%～7.92%(n=3)。该方法简单、选择性高,可实现对烟叶中三唑类杀菌剂残留的准确分析。     

对羟基苯甲酸乙酯印迹聚合物固相微萃取制备及条件优化

采用分子印迹技术,以对羟基苯甲酸乙酯(模板分子):α-甲基丙烯酸(功能单体):乙二醇二甲基丙烯酸酯(交联剂)摩尔比为1∶4∶20,反应温度为80℃,反应时间为15h,本体聚合的方法合成印迹聚合物。利用微量进样器和玻璃毛细管自制分子印迹固相微萃取装置。将自制固相微萃取与气相色谱联用,并对萃取头的萃取条件如萃取温度、萃取时间、解析时间、溶液离子强度等进行优化。通过选择性吸附实验测得,分子印迹固相微萃取对对羟基苯甲酸甲酯、对羟基苯甲酸乙酯和对羟基苯甲酸丙酯的萃取量分别为103.54、134.26和114.68μg,均大于非分子印迹固相微萃取的萃取量47.88、49.24和41.41μg,印迹萃取头表现出了良好的吸附性和选择性。     

木犀草素分子印迹聚合物的分子识别特性及固相萃取研究

采用分子印迹技术,以木犀草素为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,通过热引发聚合,制备了木犀草素分子印迹聚合物,并通过装入固相萃取柱研究了聚合物对木犀草素的选择性能.结果表明,该分子印迹聚合物对模板分子具有高度选择性和识别能力,而空白聚合物却不具备这样的特性.将木犀草素分子印迹聚合物用于固相萃取花生壳提取物,分离富集其中的木犀草素活性成分,在萃取柱上载样品之后,先用V(乙醇):V(水)=1:1溶液进行清洗,再用V(乙醇):V(水)=7:5溶液进行目标分子的洗脱,木犀草素的纯度可由1.6%提高到94.1%,回收率90.0%.木犀草索分子印迹固相萃取柱具有较好的稳定性和耐用性能,使用4次后其选择识别性能仍未降低,显示该聚合物具有直接作为复杂天然产物中木犀草素分离提取材料的潜能.     

Comparison of molecular adsorption ability of the molecularly imprinted polymers prepared by ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate as cross linkers

The target of this study was to synthesize the molecularly imprinted polymers (MIPs) of L ‐phenylalanine as the solid phases for characterization of molecular adsorption by molecularly imprinted solid phase extraction (MISPE). These MIPs, in microscale, were synthesized using thermal (40°C)‐compared with thermal (65°C)‐initiated polymerization process. Itaconic acid was chosen as the functional monomers, and either ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate (TRIM) was used as the cross linker and was compared together. The influences of several parameters on the properties of the MIPs were investigated, especially physical robustness from the percentage yields and molecular adsorption from the percentage recovery by MISPE. The best yields were obtained from polymers made using TRIM and thermal (65°C)‐initiated polymerization. However, there were no significant differences in molecular adsorption. It was concluded that these parameters can be considered to synthesize MIPs for chiral separation in advance steps such as other related chromatographic techniques. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2325–2330, 2007     

焦性没食子酸分子印迹聚合物的制备与吸附特征研究

以焦性没食子酸为模板分子,丙烯酸为功能单体,甲醇为溶剂,研究了模板分子与功能单体的结合比例,表明焦性没食子酸和丙烯酸之间通过氢键形成1∶1型配合物。在模板分子与功能单体、交联剂物质的量的比为1∶4∶20的条件下,采用沉淀聚合法制备了焦性没食子酸分子印迹聚合物微球。静态吸附实验表明,可制备出吸附量大且特异性识别能力较高的分子印迹聚合物,对焦性没食子酸有较高的亲和性和选择性。采用恒温振荡平衡吸附法以及Scatchard分析研究了聚合物的吸附特征,结果表明焦性没食子酸分子印迹聚合物在水环境下存在2种吸附位点,最大表观吸附量分别为7.5516μg/mg和11.9225μg/mg,平衡离解常数分别为9.2720×10-3mmol/L和0.1892 mmol/L。     

Synthesis and characterization of 3,4‐dihydroxyphenylacetic acid imprinted polymers

Eight molecularly imprinted polymers (MIP1–MIP8) were synthesized with different functional monomers and porogens using 3,4‐dihydroxyphenylacetic acid (DOPAC) as a template. Thermal, radical bulk polymerization was employed in the presence of ethylene glycol dimethacrylate as a cross‐linker. A computational analysis indicated that complexes with four molecules of 4‐vinylpyridine, 1‐vinylimidazole and acrylonitrile had high positive enthalpies of formation. The polymers synthesized with these monomers showed an imprinting factor below 1. Polymer MIP8 synthesized with allylamine as the functional monomer, with the highest energy of interaction with DOPAC, was characterized by the highest imprinting factor equal to 1.91. Examination of the binding ability of DOPAC and a group of structurally related compounds showed that the strong interactions between amine groups in the polymer and carboxylic groups in the analyte governed the recognition mechanism. The Langmuir adsorption model and the pseudo‐second‐order mechanism properly evaluated the MIP8 and non‐imprinted polymer 8 adsorption characteristics. Scatchard analysis revealed that MIP8 had two classes of heterogeneous binding sites with K_d(1) = 0.12 µmol L^?1 and K_d(2) = 1.46 µmol L^?1. Finally, the potential application of MIP8 for separation of DOPAC was demonstrated. Copyright © 2011 Society of Chemical Industry     

分子印迹固相萃取法提取花生壳中木犀草素

采用分子印迹技术,以木犀草素为模板分子、丙烯酰胺为功能单体、EGDMA为交联剂,合成了木犀草素印迹聚合物。将该印迹聚合物用于固相萃取,分离提取花生壳中的木犀草素。结果表明,该印迹聚合物对木犀草素具有较高的吸附性能和选择性,用印迹柱萃取得到的木犀草素纯度高出硅胶柱分离近20个百分点,达到96.2%。且MIPs-SPE柱与普通的硅胶柱相比,经过洗脱再生后可以反复使用多次。     

三聚氰胺分子印迹固相萃取小柱的研制及其应用

用本体聚合法制备三聚氰胺分子印迹聚合物,通过静态平衡吸附实验及固相萃取实验表征其固相萃取性能,结合HPLC法对实际奶粉样品中的三聚氰胺进行测定.三聚氰胺模板聚合物的吸附能力强于空白聚合物;固相萃取柱对三聚氰胺标准溶液(0.3 mmoL/L)一次性萃取率达97.01%,奶粉样品中三聚氰胺测定的平均回收率为101.2%.印...     

三唑酮分子印迹纳米球的制备及应用

建立了烟叶中8种三唑类杀菌剂残留的分子印迹固相萃取-超高效液相色谱-串联质谱（MISPE-UPLC-MS/MS）检测方法。实验中,运用计算机模拟技术筛选最佳功能单体及溶剂,并确定最优聚合反应配比,估算了TDF-MAA的自组装过程与红外光谱图,热力学分析表明TDF-MAA自组装为吸热非自发过程,预聚合反应温度拟定为30℃;采用沉淀聚合法制备了三唑酮分子印迹聚合物纳米颗粒,颗粒粒径分布均匀,平均粒径为200nm;该纳米颗粒对模板分子及其结构类似物具有良好的特异性吸附能力,针对模板分子的分离印迹因子达到2.42;将加标烟叶样品经该纳米颗粒组装的固相萃取柱进行前处理,用UPLC-MS/MS分析前处理液,烟叶中8种三唑类杀菌剂的固相萃取回收率为70.14%～105.43%,检出限为4.82～11.97ng/mL,相对标准偏差（RSD）为0.26%～2.27% （n=6）,实现了复杂基质烟叶中多种三唑类杀菌剂的同时检测。     

3,3′‐Diindolylmethane imprinted polymers: synthesis,characterization and analytical procedure for template isolation from biological matrix

A novel sorbent for the separation of 3,3′‐diindolylmethane (DIM) has been developed. DIM was used as a template molecule to prepare twelve imprinted polymers from seven different functional monomers in six various porogens in the presence of ethylene glycol dimethacrylate as a crosslinker. The binding capacity showed that the highest binding specificity was achieved when allylamine as the monomer and carbon tetrachloride as the porogen were used to form bulk polymers. Binding capacities were 130.4 ± 2.8 µg g^?1 for imprinted MIP7_a polymer versus 49.03 ± 0.44 µg g^?1 for non‐imprinted NIP7_a polymer. An imprinting factor of 3.12 reflected the high specificity of MIP7_a. A solid‐phase extraction protocol was fully optimized. Two methanol–water systems were selected as the most effective for loading and washing steps, while acetonitrile was chosen as the most efficient eluent suitable for recovery of 91.7 ± 3.8% of DIM. Optimal concentration of DIM and volume of loaded sample were also examined. A loaded volume of 2.5 mL was the most appropriate for 0.625 and 1.25 mg L^?1. The use of MIP7_a for the separations of DIM from spiked bovine serum albumin was evaluated, showing a total recovery of 87.7 ± 3.5%. The commercial sorbent C18 was not suitable for such an application. © 2013 Society of Chemical Industry     

Preparation and characterization of molecularly imprinted polymer of bovine serum albumin

Molecularly imprinted polymer beads of bovine serum albumin (BSA) were prepared via inverse phase suspension polymerization, using BSA as the template molecule, a combination of acrylamide and methacrylic acid (MAA) as double functional monomers, and N, N′‐methylene bisacrylamide as the crosslinker. The effect of different monomer ratios and degrees of crosslinking were investigated. When both selectivity and physical properties of the resultant polymer beads were taken into account, the ratio of MAA in the total monomers was chosen at 40% (m/m) and the degree of crosslinking at 30% (n/n), the resultant polymer beads had good selectivity (α = 2.77) and good physical properties. The effects of pH and temperature were studied. It turned out that the functionalization of polymers of BSA prepared via inverse‐phase suspension polymerization exhibited specific recognition for BSA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012