本体聚合法制备2-氯酚分子印迹聚合物及其性能评价

采用本体聚合法,以2-氯酚为模板分子,4-乙烯吡啶为功能单体,三羟甲基丙烷三甲基丙烯酸酯为交联剂合成了一系列分子印迹聚合物,并通过选择性实验和静态吸附实验对聚合物的选择性及吸附性能进行评价.结果显示:当以甲苯作为致孔剂,功能单体与模板分子的摩尔比为2:1时,聚合物对模板分子的印迹因子为1.71,亲和位点总数Bmax为0.1137 mmol/g,具有最优的选择性和吸附能力.     

微球形4-氨基吡啶分子模板聚合物的合成及结合性质研究

利用分子印迹技术,通过沉淀聚合方法合成了对4-氨基吡啶具有选择性结合能力的微球形分子模板聚合物.通过静态结合方法研究了该聚合物的选择性结合能力以及不同溶剂及引发剂的用量对聚合物形态及球状聚合物粒径大小的影响.底物选择性实验结果表明,与结构相似的化合物相比,4-氨基吡啶球形分子模板聚合物对4-氨基吡啶显示出强的选择性.     

农药丙溴磷分子印迹聚合物微球的制备与结合性能研究

采用分子印迹技术,以丙溴磷为模板分子,分别以α-甲基丙烯酸和丙烯酰胺为功能单体,在乙腈溶液中合成了2种对丙溴磷具有选择性结合能力的分子印迹聚合物.紫外光度法研究表明,模板分子丙溴磷与α-甲基丙烯酸之间的作用强于其与丙烯酰胺之间的作用;扫描电镜的研究则表明以α-甲基丙烯酸为功能单体合成的分子印迹聚合物呈微球形,粒径约为0.5 ～2 μm;利用平衡结合实验研究了不同功能单体制备的聚合物对模板分子的结合能力及其对底物的选择性,经Scatchard模型分析,求出了聚合物的最大表观结合量(Qmax)和平衡离解常数(Kd)分别为49.44 μmol/g 和1.05 mmol/L.研究表明以α-甲基丙烯酸为功能单体合成的分子印迹聚合物对丙溴磷表现出更强的结合能力和更高的选择性.     

对硫磷分子印迹聚合物在固相萃取中的应用

采用分子印迹技术,以对硫磷为模板分子,二乙烯三胺为固化剂,环氧树脂为单体,聚乙二醇为致孔剂,制备了具有良好识别性能的分子印迹聚合物.系统考察了对硫磷与其结构类似物在该聚合物上的选择性分离富集特性.用聚合物固相萃取了小白菜中的对硫磷.结果表明,聚合物对模板分子产生了印迹效应,对对硫磷有明显的选择性.本文采用C18色谱柱,...     

分子烙印技术简介

分子烙印技术的基本思想是源于人们对抗体—抗原或酶的专一性的认识 ,即一种抗体只能针对一种抗原 ,一种酶只能选择性的催化一种或固定的几种底物 ,而分子烙印技术则通过人工的方法合成与目标分子耦合的大分子化合物 :以目标分子为模板 ,将具有结构互补的功能化聚合物单体分子通过共价键或非共价键的方式与模板分子结合 ,加入单体进行聚合反应 ,反应完成后将模板分子提取出来后形成具有空穴的能识别模板分子的高分子。用这种基于仿生方法合成的大分子聚合物即为分子烙印聚合物 ,它与模板分子的位置 ,形状 ,官能团互补[4 ] ,对模板分子具有高…     

麻黄碱印迹聚合物合成条件对其形态及结合特性的影响

印迹聚合物合成条件对聚合物性能的影响是分子印迹技术中的一项重要研究内容。以左旋麻黄碱为印迹分子,甲基丙烯酸为功能单体,使用不同的交联剂和致孔剂合成了印迹聚合物,并对所得到的印迹聚合物的比表面积、孔结构和结合特性进行了评价。研究结果说明合成的印迹聚合物对印迹分子具有很好的亲和能力及选择性。致孔剂可以影响聚合物比表面积的大小及单体组成。氯仿是甲基丙烯酸-乙二醇二甲基丙烯酸酯和甲基丙烯酸-季戊四醇三丙烯酸酯聚合链的良溶剂,导致了比表面积及孔容较小的聚合物结构;而以乙腈为致孔剂得到的聚合物有较大的比表面积。共聚物中羧基含量的测定结果也说明,在预聚溶液中单体浓度相同的条件下,以不同的致孔剂进行合成得到的聚合物中甲基丙烯酸的比例不同。聚合物的比表面积及单体浓度的差别都可能导致聚合物的结合容量不同。     

芹菜素分子印迹聚合物的制备及印迹效率评价

采用分子印迹技术,以芹菜素为模板合成了其分子印迹聚合物,并优化了合成条件。采用平衡结合实验考察了印迹聚合物对底物的吸附性能与选择性,并对聚合物的印迹效率进行了评价。结果表明,以2-乙烯基吡啶(2-Vpy)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,四氢呋喃(THF)为致孔剂,且当n(API):n(2-Vpy):n(EDMA)=1:8:40,反应温度为60℃时,所得的芹菜素分子印迹聚合物对底物具有高吸附性能和选择性识别能力;Scatchard分析表明,在研究的浓度范围内,聚合物中形成了对模板分子有不同亲和力的两类结合位点;芹菜素印迹聚合物的印迹效率为47.9%。     

药物头孢氨苄分子模板聚合物水中结合性质的研究

采用分子模板技术合成了以头孢氨苄为模板分子以三氟甲基丙烯酸和４－乙烯基吡啶同时为功能单体的分子模板聚合物。将得到的棒状聚合物研磨过筛后,运用平衡结合实验研究了头孢氨苄分子模板聚合物的结合性质,Ｓｃａｔｃｈａｒｄ分析表明,在所研究的浓度范围内,在聚合物中形成了两类不同的结合位点。头孢氨苄分子模板聚合物与其化学组成相同的非模板聚合物相比,有很高的结合容量。底物选择性实验表明,与其它结构相似的药物相比,     

氨基安替比林分子原位烙印柱的制备及其水中结合性质的研究

实验采用原位聚合法以甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,偶氮二异丁扉(AIBN)为引发剂,正十二醇和甲苯为致孔剂直接在液相色谱柱中制备了氨基安替比林分子烙印柱．讨论了模板分子及其类似物在有机相和水相中的色谱行为及作用机理．实验表明,在水相中烙印柱具有很强的保留性能,氨基安替比林的保留因子可达到94．41．结果认为离子作用和疏水作用是使得氨基安替比林及类似物具有很强的保留性的重要原因,为研究模板聚合物的结合特性,采用前流分析法分别测定了氨基安替比林、氨基比林和安替比林在烙印柱上的吸附等温线．实验表明,分子烙印聚合物对烙印分子表现了较高的选择性,这和通过比较各物质在分子烙印柱和空白柱上保留因子所获得的结果一致．     

结晶紫分子印迹聚合物的合成及吸附性能评价

以结晶紫为模板分子,丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂合成了分子印迹聚合物。研究了致孔剂种类,交联剂用量,模板分子用量等参数对印迹聚合物吸附结晶紫性能的影响,得到该聚合反应的优化条件:结晶紫、丙烯酸和EGDMA的摩尔比为1:4:40。采用静态平衡结合法以及Scatchard分析研究了聚合物的结合特征,发现该印迹化合物存在两种结合位点,它们的离解常数分别为56.2μmol/L和7.52μmol/L。     

Molecularly Imprinted Polymer with Calix[4]arene Derivative for the Recognition of Acetanilide

Two molecularly imprinted polymers binding to analgesic acetanilide were prepared using either dual functional monomers of calix[4]arene derivative and acrylamide or single monomer acrylamide, respectively. The polymers were ground, sieved and investigated by equilibrium binding experiment to evaluate their recognition properties for the template and other substrates. Scatchard analysis showed that homogeneous recognition sites were formed in the imprinted polymer matrix. Our results demonstrated that the polymer using two functional monomers exhibited better selectivity for the template. This study may open new frontiers for the development and application of imprinted polymers, such as drug separation and purification.     

Study on the Binding Characteristic of S-Naproxen Imprinted Polymer and the Interactions between Templates and Monomers

S-naproxen imprinted polymer was prepared with acrylamide as a functional monomer, 1,4-butanediyl diacrylate as a new kind of crossliner, and 2,4,6-trimethylbenzoylphenyl-phosphinic acid ethyl ester as photoinitiator. Their UV and IR spectra were applied to study the interactions between the template and the monomer. Binding experiments showed that the S-naproxen imprinted polymer had better recognition capability for the template than that of a blank polymer. The adsorption distribution coefficient KD of S-naproxen on molecularly-imprinted polymer was 153.2 g/mL, and the separation factor was 1.95 when the initial concentration of substrate was 2.0 mmol/L. Scatchard curves suggested that there were two classes of binding sites in the imprinted polymer and only one class in the blank polymer. Computer simulation using Hyperchem showed the existence of the interactions between the template and the functional monomer as well as the models of the complexes formed by the template and the monomer.     

模板分子中作用基团的数目及位置对印迹聚合物印迹效应的影响

为了研究模板分子中作用基团的数目和位置对印迹聚合物印迹效应的影响, 分别以含有羟基数目和位置不同的羟基苯甲酸化合物3,4,5-三羟基苯甲酸(3,4,5-THBA), 3,4-二羟基苯甲酸(3,4-DHBA), 2,4-二羟基苯甲酸(2,4-DHBA)和3-羟基苯甲酸(3-HBA)为模板分子, 以丙烯酰胺为功能单体, 乙二醇二甲基丙烯酸酯为交联剂和乙腈(MeCN)为致孔剂, 采用非共价本体聚合方法制备了对应的印迹聚合物, 用色谱法评价了其分子识别性能. 结果表明, 制备的印迹聚合物对相应的模板分子均具有印迹效应, 在流动相H₂O/MeCN(体积比1/99)中, 各印迹聚合物对相应的模板分子3,4,5-THBA, 3,4-DHBA, 2,4-DHBA和3-HBA的印迹因子分别为5.51, 5.55, 2.60和2.03. 通过与同样条件下制备的龙胆酸(GA)、水杨酸(SA)和对-羟基苯甲酸(4-HBA)印迹聚合物对其模板分子印迹效应的比较发现, 模板分子中作用基团数目越多, 印迹效率越高; 模板分子中作用基团-COOH和-OH的相对位置对印迹效率影响很大, 当-COOH和-OH在苯环上处于对位时的印迹效率, 高于其处于间位的印迹效率; 当-COOH和-OH在苯环上处于邻位时, 由于形成分子内氢键会降低其印迹效率. 实验还发现, 3,4-DHBA的印迹聚合物可以实现其结构类似物3,4,5-THBA和2,4-DHBA的基线分离, 为生物活性组分3,4,5-THBA的分离和测定提供了依据.     

二茂铁甲酸分子印迹聚合物的制备和识别机理、结合特性

以二茂铁甲酸（FCA）为模板,选用不同的功能单体制备了一系列分子印迹聚合物,用平衡结合实验考察了它们对模板分子的结合性能。 结果表明,以甲基丙烯酸为功能单体制得的印迹聚合物P1对模板分子有很好的选择性,特异性吸附量ΔCP为23.18 μmol/g,印迹因子IF为2.33,竞争性结合实验结果表明,P1可以将模板分子从结构类似物中分离出来。 Scatchard方程研究表明,在研究的浓度范围内聚合物中形成了一类等价的结合位点,其对模板分子的平衡离解常数K=1.94 mmol/L,最大表观结合量Cpmax=92.33 μmol/g。 研究还表明,FCA的羧基是在聚合物的孔穴中产生识别位点的功能基,模板分子上的羧基与MAA的羧基形成双重氢键作用是分子识别的主要作用力。     

光接枝表面修饰法制备牛血红蛋白的分子印迹微球

聚苯乙烯球载体表面经引发转移终止剂修饰后, 采用光接枝表面印迹方法制备了以牛血红蛋白(BHb)为模板分子、丙烯酰胺为功能单体和N,N′-亚甲基双丙烯酰胺为交联剂的分子印迹聚合物微球(MIP). 进一步采用红外光谱(IR)、扫描电子显微镜(SEM)和元素分析对聚合物微球进行了表征, 证实了载体表面成功地接枝了分子印迹层, 并研究了其吸附性能和分子识别选择性能. 结果表明, 采用光接枝表面修饰法制备的分子印迹微球对模板分子有着很好的吸附容量和识别选择性.     

软骨藻酸分子印迹聚合物的制备及其固相萃取应用

以贝毒-软骨藻酸的结构类似物1,3,5-戊烷三羧酸为模板分子,4-乙烯基吡啶为功能单体,乙二醇二甲基双丙烯酸酯为交联剂,合成了对软骨藻酸具有较好选择性的分子印迹聚合物。经索氏提取去除模板分子后,在聚合物内部形成了与模板分子1,3,5-戊烷三羧酸以及结构类似物软骨藻酸尺寸、形状以及活性基团互补的结合位点。通过静态平衡结合实验研究了该聚合物的结合能力和选择性能,与化学组成相同的相应非印迹聚合物相比,1,3,5-戊烷三羧酸的分子印迹聚合物对软骨藻酸具有较高的吸附性能和选择性。用150mg印迹聚合物填充于1.0mL玻璃注射器制成的分子印迹固相萃取柱,采用离线模式,并结合高效液相色谱实现紫贻贝和海水中软骨藻酸的分离与检测。对于加标2mg/L的紫贻贝和海水样品,回收率分别达到(93.4±4.9)%和(89.7±3.2)%(n=3)。     

酚酞分子印迹聚合物的制备及特异吸附性能

以泻药酚酞为模板分子,4-乙烯基吡啶为功能单体制备了模板分子和功能单体不同比例的一系列酚酞分子印迹聚合物。利用扫描电镜对聚合物进行了表面形态分析,采用静态平衡实验法研究了聚合物对模板分子及其类似物的吸附行为和选择性识别能力。实验结果表明,所制备的分子印迹聚合物,吸附 3 h 后基本接近最大吸附量,其中模板分子、4-乙烯基吡啶和交联剂的摩尔比为 1∶6∶20的MIP2的印迹因子为 2.30,效果最佳。Scatchard 分析表明, 在所研究的浓度范围内,吸附过程存在两类结合位点,一类高亲和力结合位点的离解常数为Kd1= 0.63 mmol/L,最大表观结合量 Qmax1 = 25.4 umol/g,另一类低亲和力结合位点的离解常数为 Kd2 =3.5 mmol/L,最大表观结合量 Qmax2 = 61.9 umol/g,通过与酚酞类似物质在酚酞分子印迹聚合物上的吸附行为比较,表明对酚酞具有很好的选择性吸附。     

Sulfonamide imprinted polymers using co-functional monomers

Molecular imprinted polymers (MIPs) prepared using combination of acrylamide (ACM) and 4-vinylpyridine (4-Vpy) as co-functional monomers exhibited efficient recognition properties in both organic and aqueous media as HPLC stationary phase. The results indicate that amide and pyridine groups in functional monomers formed strong hydrogen-bonding interaction with the template molecule, and specific recognition sites were created within the polymer matrix during the imprinting process. When sulfamethoxazole (SMO) was used as template, a MIP prepared in a polar organic solvent (acetonitrile) using the combination of ACM and 4-Vpy showed better recognition of template than the polymer prepared in the same solvent using the combination of acidic monomer (methacrylic acid) and basic monomer 4-Vpy. On the contrary, when sulfamethazine (SMZ) was used as template, a MIP prepared using the combination of methacrylic acid (MAA) and 4-Vpy showed better recognition of template than the polymer prepared using the combination of ACM and 4-Vpy. Our results indicate that in organic media the degree of retention of the sample molecules on the imprinted polymers was controlled by the hydrogen-bonding interaction between the sample molecules and the polymer, while in aqueous media it was determined to a considerable extent by hydrophobic interactions. In both media the shape, size and the electronic structure of the template molecule were all-important factors in the recognition process.     

A molecularly imprinted polymer receptor for the enantiomeric recognition of amino acid hydantoins mimicking cooperative hydrogen bonds between nucleotide bases

Using acrylamide as hydrogen bonding functional monomer and (5R)-5-benzylhydantoin as template, a molecularly imprinted polymer was prepared in a polar solvent, which exhibited good enantiomeric recognition properties. The binding characteristics and selectivity of the polymer were evaluated by batch methods. Scatchard analysis showed that two classes of binding sites were produced in the polymer matrix and their dissociation constants were calculated to be 3.5 × 10-5mol/L and 4.3 ×10-4 mol/L, respectively, by utilizing the model of multiple independent classes of binding sites. These results were more reasonable than those obtained by Scatchard analysis , which was in agreement with the prediction of the binding characteristics of the polymer by exploring the effect of acrylamide on UV spectra of (5R)-5-benzylhydantoin. The substrate- and enantio-selectivity of the polymer was investigated. Finally, the study of effect of water on the chiral separation factor of the polymer further proved that the hy     

Influence of intramolecular hydrogen bond of templates on molecular recognition of molecularly imprinted polymers

Three molecularly imprinted polymers (MIPs) were prepared corresponding to three structurally related template compounds 4-hydroxybenzoic acid (4-HBA), gentisic acid (GA) and salicylic acid (SA) that differ in intramolecular hydrogen bonding ability using acrylamide (AA) as a functional monomer. HPLC method was used to evaluate the binding performances of the MIPs to the templates and several analogues. The results showed that the difference in their molecular recognition ability was pronounced. The highest molecular recognition ability was observed for 4-HBA-imprinted polymer. It was proved that the hydrogen bond interaction between the functional monomer and the template (4-HBA) played a major role in the recognition process and Scatchard analysis showed that two classes of binding sites were formed in 4-HBA-imprinted polymer. Their dissociation constants were estimated to be 1.76×10⁻⁴ and 1.40×10⁻³ mol l⁻¹, respectively. But for GA- or SA-imprinted polymer the molecular recognition ability was not improved compared to the blank polymer (BP). By comparison of the structures of the three templates, it was concluded that the molecular recognition ability will decrease when the template itself is able to form intramolecular hydrogen bond in the molecular imprinting process. This study will be helpful for us to understand the molecular recognition mechanism of MIPs and of instructive significance for the prediction of the selectivity of MIPs.