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。     

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。     

Interaction of molecularly imprinted polymers with creatinine

Memory sites toward clinically relevant creatinine have been imparted in polymers based on methacrylic acid, N-vinyl pyrrolidine, and 2-hydroxy ethyl methacrylate by the technique of molecular imprinting. The polymers are subjected to interaction with creatinine and creatine, a molecule of close resemblance with creatinine. The results show that selectivity is largely governed by the nature of the monomer. The reusability of the polymer is also demonstrated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2539–2542, 1997     

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     

Extraction and determination of malachite green from aquatic products based on molecularly imprinted polymers

Molecularly imprinted polymers (MIPs) were synthesized using malachite green (MG) as template, and methacrylic acid/sodium methacrylate as composite monomers. The equilibrium dissociation constant and apparent maximum adsorption capacity of the MIPs reach 12.2 mg·L^?1 and 3.2 mg·g^?1, respectively. The MIPs demonstrate excellent recognition ability due to high-affinity sites constructed by the electrostatic interaction and hydrogen bonds between template and composite monomers. The MIPs were successfully employed for the detection of MG residue in aquatic products coupled with high-performance liquid chromatography (HPLC) with a detection limit of 0.57 μg·kg^?1.     

Synthesis of hybrid magnetic molecularly imprinted polymers for the selective adsorption of volatile fatty acids from anaerobic effluents

A novel magnetic, structured (with ordered pores) and hybrid imprinted polymer (HMMIP) was synthesized to selectively adsorb volatile fatty acids (VFAs) from aqueous matrices. Usual characterization techniques showed that a mesoporous adsorbent was obtained with relatively low specific areas but that could selectively (imprinting factor of 1.64) remove isovaleric acid (used as template) from aqueous solutions and effluents containing VFAs with a good capacity (Q_e ~ 50 mg g^?1). From kinetic studies a pseudo‐nth‐order model showed the best fit to the experimental data and resulted in k _{n = 3} equal to 8 × 10^?4 g mg^?1 min^?1 whereas thermodynamic studies indicated that the adsorption of isovaleric acid onto HMMIP was endothermic and entropically driven. Reuse studies indicated that HMMIP loaded with VFA could be efficiently regenerated with acetone–water solution which led to an adsorption loss of ca 10% after three regeneration/reuse cycles and that the magnetic and specific adsorbent could be removed from complex matrices with an efficiency of ca 77%. Biochemical methane production assays showed that the addition of HMMIP to anaerobic batch reactors increased by four times the methane production due to the selective adsorption of VFAs. © 2020 Society of Chemical Industry     

磁性分子印迹聚合物的制备与应用研究

磁性分子印迹聚合物是在磁性微粒表面利用分子印迹技术合成具有超顺磁性、高选择性、高吸附性和特异性识别的聚合物。能在外加磁场作用下实现快速分离和定向移动,是一种新型高分子材料。本文主要介绍了物理法、化学法和模板法3种磁性微粒的制备方法,以及利用分子印迹技术制备磁性分子印迹聚合物,并探讨了悬浮聚合、乳液聚合和沉淀聚合3种聚合方法的研究进展,总结了磁性分子印迹聚合物在农药残留、兽药残留、重金属残留和生物医学方面的应用。分析表明磁性分子印迹聚合物在生物医学领域,尤其是抗菌治疗方面有良好的发展前景。     

分子印迹膜的研究进展

介绍了分子印迹膜的制备方法、表面形态、识别机理、传质模型;评述了分子印迹膜在手性化合物的分离、膜传感器、固相萃取、渗透汽化等方面的应用研究进展。     

分子印迹膜分离技术进展

分子印迹膜是分子印迹技术与膜分离相结合的一种新型的分离膜,具有高度的特异性分子识别能力,在分离工程中有着巨大的潜能。本文介绍了分子印迹技术的基本原理和分子印迹膜的结构特点,分析了分子印迹膜的两种传质机理,“延迟”效应和“促进”效应,简介了当前的研究及应用进展,包括了制备组成的优化手段,实现自组装的主要的合成方法、复合材料的开发以及在药物分离中的应用,提出了分子印迹膜当前存在的问题,最后对其发展进行了展望。     

pH-responsive molecularly imprinted polymer for sorption and rapid desorption of dibutyl phthalate

The pH-responsive molecularly imprinted polymers (SR-MIPs) for the removal of dibutyl phthalate (DBP) were obtained. The polymers were synthesized using methyl methacrylate, methacrylic acid, divinylbenzene, and a template mixed at different ratios allowing to optimize the process. The so-prepared SR-MIPs were evaluated at various pH values in processes of DBP sorption. The studies covered evaluation of uptake capacity, sorption kinetics, selectivity, and elution. The imprinted samples are characterized by improved factors comparing to their non-imprinted analogues, revealing also pH-sensitivity. The highest removal of DBP (130 mg g^?1) was achieved at pH = 6, while pH-driven desorption (90%) was the most efficient at pH = 8.     

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     

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     

Influence of synthesis conditions on the production of molecularly imprinted polymers for the selective recovery of isovaleric acid from anaerobic effluents

Two molecularly imprinted polymers (MIPs) – poly(methacrylic acid‐co‐TRIM) (TRIM, trimethylolpropanetrimethacrylate) and poly(acylamide‐co‐TRIM) – were synthesized in different solvents for the selective recovery of isovaleric acid (template) generated during the anaerobic digestion process. The chemical and structural characterizations of the synthetic adsorbent were carried out by Fourier transform infrared spectroscopy, TGA and porosimetry through N₂ adsorption–desorption isotherms. The selective and adsorptive performances of the imprinted polymers were evaluated by kinetic, isothermal, thermodynamic and selectivity studies and by adsorbent reuse experiments. The poly(methacrylic acid‐co‐TRIM) synthesized with dimethyl sulfoxide:chloroform presented higher selectivity and adsorption capacity for isovaleric acid in the presence of six volatile fatty acids. The kinetic results were well adjusted to the pseudo‐nth order and intraparticle diffusion models, leading to k values of 10^?4 and 6 × 10^?5 for the best synthesis of MIPs and not‐imprinted polymers, respectively. Moreover, the Sips model best described the adsorption isotherm and generated a maximum adsorption capacity of ca 209 mg g^?1 (at 25 °C). Cycles of MIP use–desorption–reuse indicated that the selective adsorbent performed better than commercial adsorbents, losing less than 3% of adsorption capacity after three cycles. © 2018 Society of Chemical Industry     

杀铃脲分子印迹聚合物制备及识别性能的研究

采用分子印迹技术,以杀铃脲为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,在四氢呋喃溶剂中制备了杀铃脲分子印迹聚合物。以平衡吸附及高效液相色谱的方法对聚合物进行了评价。印迹聚合物对模板分子有较强的吸附能力和良好的选择性,可以很好的分离模板分子及其结构类似物。     

Surface molecularly imprinted polymers based ZnO quantum dots as fluorescence sensors for detection of diethylhexyl phthalate with high sensitivity and selectivity

This work describes the preparation of molecularly imprinted polymers using ZnO quantum dots, which were used for the selective detection of diethylhexyl phthalate (DEHP). Methacrylic acid, ethylene glycol dimethacrylate, 2,2′‐azobis(2‐methylpropionitrile) and ZnO were used as functional monomer, crosslinker, initiator and optical material, respectively. Molecularly imprinted polymers were successfully synthesized, and the linear relationship between fluorescence intensity and amount was from 0.5 to 40 µmol L^?1 for DEHP. The coefficient of correlation was 0.9923 and the imprinting factor was 11.16. The results were above 97.50% and relative standard deviation below 3.86% for the detection of DEPH in actual water samples. This study could provide a novel method using molecularly imprinted polymers for highly selective and sensitive detection of DEHP. © 2018 Society of Chemical Industry     

Synthesis of molecularly imprinted polymers for amino Acid derivates by using different functional monomers

Fmoc-3-nitrotyrosine (Fmoc-3-NT) molecularly imprinted polymers (MIPs) were synthesized to understand the influence of several functional monomers on the efficiency of the molecular imprinting process. Acidic, neutral and basic functional monomers, such as acrylic acid (AA), methacrylic acid (MAA), methacrylamide (MAM), 2-vinylpyridine (2-VP), 4-vinylpyridine (4-VP), have been used to synthesize five different polymers. In this study, the MIPs were tested in batch experiments by UV-visible spectroscopy in order to evaluate their binding properties. The MIP prepared with 2-VP exhibited the highest binding affinity for Fmoc-3NT, for which Scatchard analysis the highest association constant (2.49 × 10(4) M(-1)) was obtained. Furthermore, titration experiments of Fmoc-3NT into acetonitrile solutions of 2-VP revealed a stronger bond to the template, such that a total interaction is observed. Non-imprinted polymers as control were prepared and showed no binding affinities for Fmoc-3NT. The results are indicative of the importance of ionic bonds formed between the -OH residues of the template molecule and the pyridinyl groups of the polymer matrix. In conclusion, 2-VP assists to create a cavity which allows better access to the analytes.     

热聚合制备左旋氧氟沙星分子印迹聚合物的条件

以左旋氧氟沙星(LVFX)为模板,以α-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,采用热聚合方式,通过条件优化获得了对左氧氟沙星有特异选择性吸附的分子印迹聚合物(M IPs)。最优化条件为n(LVFX)∶n(MAA)∶n(EDMA)=1∶4∶15,聚合温度60℃,聚合时间48 h,溶剂氯仿,用量10 mL。通过结合实验分析,在最优化条件下制得的M IPs对左氧氟沙星具有很好选择性和吸附能力,分离因子α(LVFX/OLFX)为1.56。     

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。     

罗丹明B分子印迹聚合物的制备及分子识别性能研究

以三苯甲烷类碱性染料罗丹明B为模板分子,丙烯酰胺为功能分子,N,N-亚甲基双丙烯酰胺(MBA)为交联剂,采用表面修饰分子印迹法,制备对罗丹明B具有特定亲和选择性的分子印迹聚合物。应用红外光谱对印迹聚合物进行表征,通过静态吸附实验对聚合物的吸附动力学进行分析,采用平衡结合实验评价了分子印迹聚合物的吸附性能。结果表明,采用表面修饰分子印迹法所制备的印迹聚合物对罗丹明B表现出较好的特异吸附,对模板分子最大吸附量值为96μmol/g。