四环素分子印迹聚合物的制备及吸附性能研究

以甲基丙烯酸(MAA)为功能单体,乙腈为溶剂,三羟甲基丙烷三甲基丙稀酸酯(TRIM)为交联剂,通过热聚合法合成了四环素为模板的分子印迹聚合物(MIPs).采用FE-SEM、FT-IR对MIPs和非印迹聚合物(NIPs)进行了表征,考察了引发剂和溶剂的用量对MIPs产量和吸附容量的影响,研究了MIPs和NIPs的静态吸附...     

牺牲硅胶法制备烟酸分子印迹聚合物及其性能研究

选用薄层层析硅胶作为牺牲载体,以烟酸为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了烟酸分子印迹聚合物(MIPs).通过考察功能单体种类及用量、交联剂用量及硅胶用量确定了制备MIPs的最佳工艺条件,制备得到的MIPs吸附容量达到78.5 μmol·g-1.以烟酰胺作为竞争底物考察MIPs的特异吸附性...     

虚拟模板印迹法制备苯酚分子印迹聚合物用以吸附微量甲苯

甲苯是一种缺乏印迹位点的小分子,为实现对甲苯的印迹,以甲基丙烯酸为单体分子,苯酚为模板分子,二乙烯基苯作为交联剂,采用沉淀聚合法制备虚拟模板苯酚分子印迹聚合物(MIPs).通过改变溶剂用量、交联剂与单体分子的配比等方式考察了苯酚分子印迹聚合物最佳成球条件并最终制备出粒径均匀的苯酚分子印迹聚合物.之后使用该苯酚印迹聚合物与课题组前期制备的苯胺分子印迹聚合物进行了结构、形貌和吸附性能的对比,验证了虚拟模板分子印迹聚合物对甲苯分子实现特异性吸附的可行性.经气相色谱仪表征,该分子印迹聚合物对甲苯的吸附能力为6.78 mg·g-1,优于苯胺分子印迹聚合物的1.89 mg·g-1.     

苯酚分子印迹聚合物及印迹膜的制备与性能研究

以苯酚为印迹分子,2-乙烯基吡啶为功能单体,采用正交试验设计,改变功能单体种类、致孔溶剂种类、交联剂用量等影响因素,分别制备了9个苯酚分子印迹聚合物（MIP1-9）,优化得到了印迹聚合物制备的最佳条件,并在此基础上制备了苯酚印迹复合膜（MIM）。对优化得到的MIP4及MIM分别进行了吸附和渗透特性研究。结果表明,实验制备的MIP4及MIM具有一定的选择性分离富集苯酚的性能。     

磁性分子印迹聚合物微球对非那西丁的吸附性能研究

本文以双键修饰的超顺磁氧化铁为模板,以非那西丁为模板分子,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,2,2偶氮二异丁腈为引发剂,以甲苯为溶剂,70℃下通过表面印迹法制备了磁性分子印迹聚合物(Magnetic molecularly imprinted polymer,MIPs)。以MIPs为固相萃取剂,分别考察了初始浓度、吸附剂用量、温度对吸附量的影响。     

氧乐果分子印迹聚合物的制备与性能研究

以氧乐果为模板分子,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),考察了氧乐果、敌敌畏及甲胺磷在氧乐果分子聚合物上的选择性分离富集特性.用氧乐果分子聚合物固相萃取了蔬菜和天然水中的氧乐果.结果表明,聚合物对模板分子产生了印迹效应,对氧乐果有明显的选择性.流速为1.0 mL/min,进样量为20 μL.     

溶剂对分子印迹聚合物分子识别能力的影响：实验研究与计算量子化学分析

以茶碱为印迹分子，甲基丙烯酸为功能单体，二甲基丙烯酸乙二醇酯为交联剂，以氯仿、二甲基亚砜和四氢呋喃为溶剂，合成了分子印迹聚合物并测定了其对茶碱分子的识别能力，实验结果显示，在氯仿中合成的MIPs的分子识别性能最佳.综合Scatchard分析吸附行为、¹H NMR测定氢键以及量子化学中的密度泛函计算印迹分子和单体分子的溶剂化能等方法，研究聚合反应的溶剂体系对于印迹聚合物分子识别能力的影响及其作用机制.计算结果显示：采用与印迹分子和单体相互作用力较弱的溶剂体系所合成的印迹聚合物具有较高的分子识别性能.这与¹H NMR分析结果和吸附测定实验结果具有一致性.上述结果表明，溶剂对于分子印迹聚合物的分子识别性能具有重要的影响，而计算量子化学分析对于分子印迹介质合成时的溶剂体系选取和优化具有很好的指导作用.     

3,5,7,3＇,4＇,5＇-六羟基黄酮分子印迹聚合物制备及性能表征

采用分子印迹技术合成了对3,5,7,3＇,4＇,5＇-六羟基黄酮具有高效选择性的分子印迹聚合物,通过静态吸附的方法,利用Scatchard模型,研究了分子印迹聚合物的特异性识别能力。实验表明,以甲基丙烯酸为功能单体,在甲苯溶剂中聚合得到的分子印迹聚合物对3,5,7,3＇,4＇,5＇-六羟基黄酮具有较大的吸附富集能力和识别特性。其饱和吸附容量达到30.8 mg/g。     

三硝基甲苯分子印迹电化学传感器的制备和应用

以三硝基甲苯（TNT）为模板分子，甲基丙烯酸（MAA）为功能单体，采用乳液聚合法制备TNT的分子印迹聚合物（MIPs）。将制备的MIPs分散在溶剂中，通过表面涂覆法制备出检测TNT的分子印迹电化学传感器。紫外光谱表明TNT与MAA之间存在相互作用力，有助于形成结构稳定、亲和性强的MIPs。利用扫描电镜观测不同制备条件下印迹聚合物的表观形貌，发现溶剂用量为30mL、乳化剂用量为12mg时制备的聚合物形貌较优异。吸附实验表明MIPs对TNT的吸附量随着TNT初始浓度的增加而增加，140min后达到最大吸附量的95%。MIPs对TNT的分离常数远大于RDX和DNT，对RDX和DNT的选择性系数均达到4.4以上，说明MIPs对TNT有较好的选择性吸附能力。铁氰化钾探针实验和对TNT的响应曲线验证了电化学传感器的成功制备，该传感器富集3min就达到了最大电流值的94%，5min内达到吸附平衡。TNT浓度在0.1~5mg/mL的范围内与峰电流有良好的线性关系，检出限为0.06mg/mL。MIPs传感器对TNT的电流响应分别为DNT和RDX的3.13倍、3.27倍，说明其对TNT分子具有很强的特异性识别能力。     

以b-环糊精、2-羟丙基-b-环糊精和4-乙烯吡啶为功能单体制备氟比洛芬分子印迹聚合物及其吸附特征

以b-环糊精(β-CD)、2-羟丙基-β-环糊精(HP-β-CD)和4-乙烯吡啶(4-VP)为功能单体,以氟比洛芬为模板分子,以环氧氯丙烷和乙二醇二甲基丙烯酸酯为交联剂,采用本体聚合法制备分子印迹聚合物(MIPs),对氟比洛芬与功能单体的相互作用和MIPs的结构进行了表征,比较了3种MIPs对氟比洛芬的吸附性能. 结果表明,β-CD, HP-β-CD和4-VP与氟比洛芬之间以较强的相互作用形成复合物,通过交联、聚合形成聚合物,以HP-β-CD作功能单体所得聚合物印迹效果最佳,具有较强的特异性吸附能力,印迹因子和特异性吸附率分别为1.79和38.92%,分子印迹机制是β-CD的锥筒包结作用和羟丙基的亲和作用形成印迹空穴.     

Synthesis and characterization of high selective molecularly imprinted polymers for bisphenol A and 2,4-dichlorophenoxyacetic acid by using supercritical fluid technology

Molecularly imprinted polymers (MIPs) have been extensively used in chemical and biochemical related areas due to their high molecular recognition affinity and selectivity for the target molecule. On the other hand, supercritical polymerization is relatively novel technique, which can be applied in the polymerization without hazard organic solvent. This work introduces a supercritical fluid polymerization technique for preparation of MIP particles. The adsorption properties of prepared MIP particles are also investigated. The MIPs were prepared with methyl methacrylate (MMA) as a third monomer, methacrylic acid (MAA) as a functional monomer, templates (bisphenol A (BPA) and 2,4-dichlorophenoxyacetic acid (2,4-D)), methyl methacrylate (MMA) as a third vinyl monomer and ethylene glycol dimethacrylate (EGDMA) as a cross-linker. Equilibrium binding experiments are conducted to evaluate the binding characteristics of MIPs and templates (BPA and 2,4-D). The Scatchard plot analysis demonstrates that two classes of binding sites are formed with the equilibrium dissociation constants. The adsorption ability of the MIPs was also evaluated by measuring the adsorbed amounts of a similar imprinted template structure, the selectivity factor (α), and the imprinting-induced promotion of binding (IPB).     

Molecular dynamics simulations of molecularly imprinted polymer approaches to the preparation of selective materials to remove norfloxacin

A novel molecularly imprinted polymer (MIP) designed by molecular dynamics (MD) simulations was successfully prepared with norfloxacin as a template molecule, methyl acrylic acid as a functional monomer, and ethylene glycol dimethacrylate as a crosslinker. According to the theoretical prediction and experimental preparation methods, three kinds of molecular imprinting materials were designed and synthesized with MD simulations and molecular imprinting technology. The best ratio of the template to the functional monomer to the crosslinker was 1:8:40 in these studies. The experimental results illustrate that the MD simulations were credible in compounding the components of the MIPs. The structure of the prepared polymers were characterized with various methods. To analyze the adsorption performances, many kinds of static adsorption tests, including kinetic, isotherm, and selectivity tests, were used. The results indicate that the novel adsorbents conformed to the pseudo–second‐order kinetic equation and followed the Langmuir isotherm model. The adsorption amounts of MIP2 at a ratio of 1:8:40 were about 29.35 mg/g at 298 K_. The selective adsorption and reusable performance of norfloxacin were excellent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42817.     

Configuration of molecular imprinted polymer for electrochemical atrazine detection

This paper addresses the specific ability of molecular imprinted polymers (MIPs) to bind the template. MIPs for atrazine with various monomer:template and crosslinker:template ratios were prepared using bulk polymerization process. In order to obtain conditions closer to real wastewater test cases, the degree of the imprinting factor by the selection of solvent (methanol and water) was studied and compared. The polymer tested in methanol did not demonstrate good recognition of atrazine. In addition, the imprinting factors increased significantly when the imprinted polymers were tested in water solvent by 45%. Based on Scatchard analysis, the MIP was dependent upon low atrazine concentration (up to 40 mg/L) as the cavities formed in the MIP proved the cavities effects. An electrochemical analysis was done in order to prove that the method can be used as a quantitative analysis of atrazine concentration detection in water solution.     

Synthesis and characterization of methacrylic acid‐based molecular imprinted polymers by positron lifetime spectroscopy

Three molecular imprinted polymers (MIPs) were prepared with different amounts of crosslinker (ethylene glycol dimethacrylate) in methacrylic acid functional monomer. Positron lifetime spectroscopy has been used to study the variation in free volume cavities (nanosize pores) in these MIPs of different monomer‐crosslinker ratio. The changes in free volume cavities after the template molecule 4‐chlorophenol extracted from the polymer matrix were measured. The results indicate that the optimum monomer‐crosslinker ratio for this MIP is 1:5. The free volume distribution derived from CONTIN program further reveals the presence and absence of template molecules in the system. The Fourier transform infrared spectra results have been used to compliment this through the absence of stretching frequencies at 648 cm^?1 and 825 cm^?1 of C? Cl suggesting the successful extraction of the template from the MIPs. Scanning electron microscope (SEM) scans indicate the grains are of heterogeneous shape and size in agreement with earlier studies. POLYM. ENG. SCI., 54:667–674, 2014. © 2013 Society of Plastics Engineers     

溶胶-凝胶法制备鞣花酸表面分子印迹聚合物

采用溶胶-凝胶方法和表面分子印迹技术，以二氧化硅为载体，鞣花酸为模板分子，3-氨丙基三乙氧基硅烷为功能单体，四乙氧基硅烷为交联剂，在室温下合成鞣花酸分子印迹聚合物(MIPs)。通过扫描电镜表征了MIP的表面形貌。通过静态吸附实验评价了MIP对鞣花酸的吸附行为。结果显示，MIP对鞣花酸可在40 min内达到吸附平衡，印迹因子为2.68，饱和吸附容量可达70 mg/g；与非印迹聚合物相比，MIP对鞣花酸具有高选择性和特异识别性。对吸附数据进行非线性拟合结果显示，MIP对鞣花酸的吸附动力学较好地符合准二级动力学模型，MIP对鞣花酸的吸附等温线较好地符合Langmuir等温方程。另外，该材料在经过5次循环利用之后，对鞣花酸的吸附容量仍能保持在90%以上，表现了较好的重复利用性能。所合成的MIP能够作为一种良好的选择性吸附鞣花酸的功能材料，有望应用于复杂基质中鞣花酸的分离和纯化。     

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。     

Fabrication of ordered microporous styrene‐acrylonitrile copolymer blend imprinted membranes for selective adsorption of phenol from salicylic acid using breath figure method

Highly selective, ordered microporous molecularly imprinted membranes (MIMs) for phenol were synthesized by breath figure (BF) method using styrene‐acrylonitrile copolymer (SAN) as the membrane matrix and molecularly imprinted polymer nanoparticles (nano‐MIPs) as the imprinted nanoparticles. The nano‐MIPs were synthesized by oil‐in‐water emulsion polymerization using 4‐vinyl pyridine (4‐VP), methyl methacrylate (MMA) or cinnamic acid (CA) as the functional monomer, respectively. The prepared nano‐MIPs were characterized by transmission electron microscope (TEM) and Raman, whereas MIMs were characterized by SEM, membrane flux, and selective adsorption experiments. Morphological analysis exhibited that the addition of nano‐MIPs improved the formation of ordered and well‐defined porous membrane morphology. Compared with MMA‐MIM and CA‐MIM, the 4‐VP‐MIM exhibited higher membrane flux, adsorption capacity, and stronger selective binding for phenol as well as excellent permeation selectivity for phenol. Moreover, the selective effect of 4‐VP‐MIM on phenol was strongly affected by the amount of 4‐VP imprinted nanoparticles (nano‐4‐VP‐MIPs). The experimental data revealed that the 4‐VP‐MIM containing 2.0 wt % of nano‐4‐VP‐MIPs exhibited the highest separation selectivity for the template phenol, whose selectivity coefficients for phenol relative to salicylic acid (SA) and p‐hydroxybenzoic acid (p‐HB) were 5.6770 and 5.5433, respectively, which was close to the predicted selectivity coefficient value. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42350.     

RNA nucleoside recognition by phthalocyanine-based molecularly imprinted polymers

Highly selective molecularly imprinted polymers (MIPs) having a phthalocyanine-based recognition centre as receptors for RNA nucleoside were prepared. In particular, a zinc phthalocyanine peripherally substituted with methacrylic groups was synthesized and utilized as functional monomer in combination with methacrylic acid (MAA) to form polymers with the aim to obtain MIPs having improved binding capacity and selectivity for nucleosides. Tri-O-acetyladenosine (TOAA) was utilized as model template in the preparation of the MIPs. The corresponding non metallated phthalocyanine was also prepared and used as functional monomer for the preparation of the MIPs in order to understand the role of the Zinc(II) ion in the binding capacity of the polymers towards the template molecule. The MIP prepared by using both the zinc phthalocyanine and MAA showed higher binding ability towards TOAA compared to the MIPs prepared using only MAA or its combination with the non metallated phthalocyanine. The results obtained suggest that the nucleoside is specifically bound to the polymer through multi-point interactions involving both the coordination of the nucleoside to the metal of the phthalocyanine and hydrogen bonding/electrostatic interactions with MAA and the modifiers linked to the phthalocyanines. As for the selectivity, the MIPs exhibited relative high binding affinities for TOAA while they did not show any binding capacity for the other RNA nucleosides.     

Separation of hydroxybenzoic acid isomers using the molecular imprinting technique

Molecular imprinting polymers (MIPs) for salicylic acid (SA), 3‐hydroxybenzoic acid (3HBA), and 4‐hydroxybenzoic acid (4HBA) were synthesized using styrene and 4‐vinylpyridine (4‐VPy) as functional monomer and divinylbenzene (DVB) as crosslinker. The adsorption characteristics of hydroxybenzoic acid (HBA) isomers on each MIP were investigated. The materials used for the polymerization of each 3HBA and 4HBA‐MIPs were adsorbed relatively well. This verifies that the MIPs that can adsorb template selectively were synthesized. However, SA‐MIP had no molecular imprinting effect. SA has intramolecular hydrogen bond and it is difficult to adsorb on recognition site of SA‐MIP, because its structure differs from that of recognition site of SA‐MIP. It indicates that SA‐MIP had no recognition effect. 1,2,3,4‐Tetrahydro‐1‐naphthol (THN)‐MIP was synthesized, which is similar to SA with intramolecular hydrogen bond. SA was separated selectively using THN‐MIP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007