啶虫脒分子烙印聚合物的识别特性

利用分子烙印技术,以啶虫眯为模板分子,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,合成了对啶虫脒具有高度选择性的模板聚合物,通过平衡吸附实验,评价了其对啶虫眯的亲和力和选择性.与空白烙印聚合物相比,对啶虫脒表现了很高的亲和力.Scatchard分析表明,在啶虫脒模板聚合物中存在对啶虫脒有不同亲和力的两类作用位点,高亲和力的吸附位点的离解常数为Kd1=4.68×10-4mol/L,最大表观吸附量QMAX1=18.8μmol/g,低亲和力位点的离解常数为Kd2=7.93×10-3mol/L,最大表观吸附量QMAX2=142μmol/g.通过与啶虫脒类似物质在啶虫脒模板聚合物上的吸附行为比较,表明对啶虫脒具有很好的选择性.     

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．     

以桑色素为模板的分子烙印聚合物的制备、结合特性及其在薄层色谱固定相方面的应用

以桑色素为模板,选用不同的功能单体和致孔剂制备了一系列分子烙印聚合物,采用结合实验考察了它们对底物的吸附特性,发现以丙烯酰胺为功能单体,以乙酸乙酯为致孔剂制得的烙印聚合物对底物有很好的选择性,同时对一些结构相似的化合物具有一定的结合力.Scatchard方程研究结果表明,在研究的浓度范围内聚合物形成了一类等价的结合位点,其平衡离解常数为0.877mmol/L,对模板分子的最大表观结合量为59.18μmol/g.可认为桑色素分子中3,7,4'位的羟基与功能单体的氢键作用是分子烙印聚合物具有底物选择性的主要因素.以该分子烙印聚合物为薄层色谱固定相,可以把模板分子从结构相似的化合物中分离出来,最小分离度为1.19.     

分子烙印聚合物作超临界流体萃取后处理用固体吸附剂

利用离线超临界流体萃取与高效毛细管电泳相结合，分析了标准添加样品中的除草剂（2，4－二氯苯氧乙酸（2，4－D）），探讨了温度、压力和改性剂对萃取的影响，考察了在不同条件下合成的2，4－D为烙印分子的子烙印聚合物对2，4－D在不同极性溶剂中的吸附能力，并将分子烙印聚合物作为超临界流流体萃取后处理用固体吸附剂，结果表明，在甲醇和水的混合极性溶剂中制备的分子烙印聚合物对提高分析选择性的效果最佳。     

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%。     

原位聚合法制备氨基安替比林分子烙印聚合物及分离特性的研究

以氨基安替比林为模板分子,采用原位聚合法制备了具有特定识别性能的棒状分子烙印聚合物。通过考察烙印分子的化学基团对分离的影响,以及离子作用和氢键作用在分离中的贡献,论证了分子烙印聚合物选择性专一的作用机理。结果表明,这种棒状聚合物对模板分子及其类似物有很好的分离能力。     

分子烙印聚合物固定相分离咖啡因和茶碱的研究

分子烙印是一种新兴的分子识别技术,利用该技术可制备对烙印分子具有“预定”识别能力的高分子聚合物,即分子烙印聚合物（MIP）,从而可以对性质和组成相近的组如对映体等进行分离^[1,2],咖啡因与茶碱的分子烙印聚合物的制备以及二者分析已有报道^[3-9],但存在两种完全相反的结论。一种观点认为,即使以咖啡因为烙印分子,所制备的聚合物对咖啡因分子的选择性吸附能力也小于茶碱^[3-6]。而另一种观点则认为,在一定条件下,如以咖啡因分子为烙印分子的烙印聚合物对咖啡因分子具有更强的吸附能力^[7-9]。本文分别采用茶碱和咖啡因作为烙印分子,以甲基丙烯酸等为功能单体,在不同条件下制备了多种非共价型分子烙印聚合物,并系统地考察了其作 为HPLC固定相对咖啡因和茶碱的分离能力,同时也对烙印分子应具备的条件加以探讨。     

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。     

氧化石墨烯基异丙隆分子印迹聚合物的制备及其吸附性能研究

以氧化石墨烯为载体,异丙隆为模板分子,采用表面印迹技术制备了分子印迹聚合物。采用透射电子显微镜、拉曼光谱和热重分析仪对该分子印迹聚合物的结构进行了表征,并通过动态平衡结合法研究了该分子印迹聚合物的吸附能力。结果表明:准二级动力学模型很好地拟合了吸附动力学,相关系数(R2)为0.999 7;与非分子印迹聚合物相比,制备的印迹材料表现出高吸附效率和快速的吸附动力学;选择性吸附试验表明该分子印迹聚合物对异丙隆具有选择性和特异性吸附。     

氨基三唑分子印迹聚合物的制备及性能表征

采用分子印迹技术,以氨基三唑(AMI)为模板分子,异丁醇为溶剂,甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酯(EDMA)为交联剂,合成了氨基三唑分子印迹聚合物(AMI-MIP)。采用静态平衡结合实验和选择性实验评价了AMI-MIP对底物分子的结合特性及分子识别性能,并进行了吸附动力学研究。结果表明,AMI-MIP对AMI存在不同亲和力的两类结合位点,且对AMI具有很高的选择吸附特性和良好的分子识别性能,AMI-MIP对AMI的吸附行为可用准二级吸附动力学方程加以描述。     

A computational model for selectivity evaluation of 2-(3,4-dimethoxyphenyl)ethylamine (homoveratrylamine) imprinted polymers towards biogenic compounds

A computational model was proposed to evaluate the affinity and selectivity of 2-(3,4-dimethoxyphenyl)ethylamine (homoveratrylamine) imprinted polymers. Four functional monomers: methacrylic acid, 1-vinylimidazole, 4-vinylpyridine, and allylamine were taken into account. Two dielectric constants were used for solvent simulations: a value of ?=2.38r(ij) for toluene was used in the analysis of prepolymerization complexes, and a value of ?=36r(ij) for methanol-water was used in the investigations of adsorption. Theoretical analysis predicted the highest affinity for the polymer synthesized from methacrylic acid. Experimental results confirmed the finding. The prepolymerization complex formed by homoveratrylamine and four methacrylic acid molecules was used to design the polymer cavity. The selectivity of the polymer was analyzed as a simulation of adsorption of six compounds in the cavity by docking procedure. Selected compounds are structurally related to the template or can be present in biological samples. The designed polymer has high selectivity towards homoveratrylamine. The proposed computational procedure could be used for successful evaluation of the imprinted polymers.     

Molecularly imprinted polymer using beta-cyclodextrin as functional monomer for the efficient recognition of bilirubin

Bilirubin (BR) imprinted polymer was successfully prepared using supramolecular host compound β-cyclodextrin (β-CD) as functional monomer. The adsorption equilibrium was attained in about 4 h, which indicated that the adsorption kinetics was comparatively fast. The results of adsorption and selectivity experiments indicated that BR-imprinted β-CD polymer was able to bind BR specifically and reversibly. The specific recognition of BR-imprinted β-CD polymer for BR may be due to the cooperative effects of inclusion interaction and hydrogen bonding. This BR-imprinted β-CD polymer was further applied to eliminate BR in human serum sample. It was verified that the binding specificity of the BR-imprinted polymer for BR was essentially sufficient in the presence of other compounds coexisting in serum sample. Therefore, as a reusable material possessing high affinity and selectivity, BR-imprinted β-CD polymer has a potential application perspective as a clinical hemoperfusion material.     

Preparation and Adsorption Characteristics of Cordycepin Molecularly Imprinted Polymers

The separation of a molecularly imprinted polymer for cordycepin was investigated. The synthesis employed cordycepin as the molecular template, alpha-methylacrylic acid as the functional monomer, glycol dimethyl acrylate as the cross-linking agent, azobisisobutyronitrile as the initiator, and tetrahydrofuran as the solvent and pore-foaming agent. The interaction between cordycepin and the functional monomer was investigated by ultraviolet-visible and infrared spectroscopy. The properties of the molecularly imprinted polymer were analyzed by scanning electron microscopy, equilibrium adsorption experiments, and the Scatchard equation. Static adsorption, solid phase extraction, and high-performance liquid chromatography experiments were employed to evaluate the adsorption properties and selective recognition characteristics. The results showed that the molecularly imprinted polymer had specific adsorption with cordycepin, and the maximum absorption capacity was 1920 µg/g. Scatchard analysis suggested that high affinity and low affinity binding sites were present. For the high affinity case, the dissociation constant and apparent maximum numbers of the binding sites were 0.0089 mmol/L and 4.78 µmol/g, respectively. The dissociation constant and apparent numbers of binding sites were 0.035 mmol/L and 6.047 µmol/g for the low affinity sites. Compared with the corresponding nonimprinted polymer, the cordycepin molecularly imprinted polymer exhibited higher adsorption and selectivity for cordycepin than structural analogs.     

Synthesis and characterization of bisphenol-A imprinted polymer as a selective recognition receptor

Molecularly imprinted polymers (MIPs) are currently used to provide selectivity in chemical sensors. In this context, a non-covalent bisphenol-A (BPA)-imprinted polymer using 4-vinylpyridine (4-Vpy) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as crosslinker and a low volatile solvent, triethylene glycol dimethyl ether (TRIGLYME), in combination with a non-reactive linear polymer, poly (vinyl acetate) (PVAc), as porogen, was synthesized with a simple polymerization procedure. Batch rebinding experiments were carried out to evaluate the binding and selectivity properties of the BPA-MIP. The experimental adsorption isotherms were fitted and a heterogeneous distribution of the binding sites was found. The selectivity of MIP demonstrated higher affinity for target BPA and BPA-analogues over other common water pollutants. The adsorption kinetics followed the pseudo-second-order kinetic model so that the specific adsorption in the imprinted cavities by two strong hydrogen bonds could be described as a chemisorption process. The diffusion mechanism was determined by the intra-particle diffusion and Boyd models, both of them revealing that the adsorption was mainly governed by intra-particle diffusion. MIP was shown to be promising for regeneration without significant loss in adsorption capacity.     

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。     

Selective Adsorption of Co(Ⅱ)by Mesoporous Silica SBA-15-Supported Surface Ion Imprinted Polymer:Kinetics,Isotherms,and Thermodynamics Studies

A novel surface ion imprinted adsorbent [Co(II)‐IIP] using polyethyleneimine (PEI) as function monomer and ordered mesoporous silica SBA‐15 as support matrix was prepared for Co(II) analysis with high selectivity. The prepared polymer was characterized by Fourier transmission infrared spectrometry, scanning electron microscopy, X‐ray diffraction and nitrogen adsorption‐desorption isotherm. Bath experiments of Co(II) adsorption onto Co(II)‐IIP were performed under the optimum conditions. The experimental data were analyzed by pseudo‐first‐order and pseudo‐second‐order kinetic models. It was found that the pseudo‐second‐order model best correlated the kinetic data. The intraparticle diffusion and liquid film diffusion were applied to discuss the adsorption mechanism. The results showed that Co(II) adsorption onto IIP was controlled by the intraparticle diffusion mechanism, along with a considerable film diffusion contribution. Langmuir, Freundlich and Dubinin‐Radushke‐ vich adsorption models were applied to determine the isotherm parameters. Langmuir model fitted the experiment data well and the maximum calculated capacity of Co(II) reached 39.26 mg/g under room temperature. The thermodynamic data were indicative of the spontaneousness of the endothermic sorption process of Co(II) onto Co(II)‐IIP. Co(II)‐IIP showed high affinity and selectivity for template ion compared with non imprinted polymer (NIP).     

橙皮苷印迹聚合物的识别性能及机理研究

为了制备对橙皮苷(HES)具有特定识别能力的吸附材料,以HES为模板分子,丙烯酰胺(AM)为功能单体,甲基丙烯酸乙二醇酯(EDMA)为交联剂,在甲醇中制备了HES印迹聚合物(MIP),采用平衡吸附实验方法研究了聚合物的吸附性能和选择性能,探讨了聚合物的印迹机理和识别机理.结果表明,MIP对HES具有较高的亲和性和选择性.当HES浓度为0.048 mmol/L时,MIP及相应NMIP对HES的分配系数KD分别为10.17 和2.973,印迹因子α达到3.421.MIP对结构相似物芦丁及柚皮苷的选择因子β分别为2.446和1.246.机理研究表明识别位点来自AM与HES苯甲酰系统的氢键作用,吸附溶液中水含量的增加对MIP的识别能力有较大的影响.最后,以高效液相色谱研究了MIP在样品中的分离富集能力,表明该印迹聚合物具有一定的应用潜能.     

A NOVEL MOLECULARLY IMPRINTED POLYMER： SYNTHESIS AND ADSORPTION BEHAVIOR OF GATIFLOXACIN

A kind of molecularly imprinted polymer （MIPs） with high selectivity was prepared using methacrylic acid （MAA） as functional monomer, ethylene glycol dimethacrylate （EDMA） as crosslinker and Gatifloxacin as template. The effect of various parameters such as volume of solvent, functional monomer dosage, crosslinker dosage and polymerization time were investigated. The selective binding experiment for substrates show that the affinity and selectivity for Gatifloxacin were higher than that for blank polymer. Scatchard analysis show that the MIPs recognized template with two kinds of binding sites. The dissociation constant Kd and maximum adsorption quantity Qmax of these two kinds of binding sites were calculated： Kd1 and Qmax1 of the binding sites with high affinity were 8.67×10^-4 mol/L and 28.19μmol/g, while Kd2 and Qmax2 of the binding sites with low affinity were 1.05×10^-3 mol/L and 33.20μmol/g respectively.     

铅离子印迹固相萃取原子吸收光谱分析

以Pb2+为模板,丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用本体聚合技术,制备了对Pb2+具有特异性识别作用的离子印迹材料。通过红外光谱,吸附容量,干扰实验等讨论了该离子印迹材料的相关性质。结果表明,该离子印迹材料对Pb2+的结合能力明显强于非印迹材料,能够很好的排除其他金属离子的干扰。通过制备该离子印迹材料,能够富集水体中的痕量铅,结合原子吸收光谱法对其进行定量分析,为测定复杂环境样品中痕量铅离子提供一个高选择性,高预富集效率的固相萃取材料和分析方法。