单步溶胀聚合法制备单分散分子印迹聚合物微球

用无皂乳液聚合法制得的微米级聚苯乙烯微球为种球,以N-甲基天门冬氨酸(NMA)为模板分子,通过单步溶胀聚合法在水相中制备了单分散分子印迹聚合物微球(MIPMs)。研究了影响种球溶胀的因素,并对MIPMs的结构进行了表征。实验表明,单步溶胀聚合法能够制得粒径2~3μm、单分散性好的MIPMs,且具有较好的特异吸附性能。Scatchard分析表明,MIPMs在识别NMA过程中存在两类结合位点,计算得到高亲和力的结合位点的离解常数KD1和最大表观结合常数Bmax1分别为0.223 mmol/L和2.12μmol/g,低亲和力的结合位点的离解常数KD2和最大表观结合常数Bmax2分别为5.34 mmol/L和36.42μmol/g。     

邻苯二甲酸二丁酯分子印迹聚合物的制备及性能研究

以邻苯二甲酸二丁酯(DBP)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(EGD-MA)为交联剂,采用沉淀聚合法制备了分子印迹聚合物。通过静态平衡结合法和Scatchard分析法,研究了分子印迹聚合物的识别性能和结合能力。结果表明,该分子印迹聚合物对模板分子DBP具有较强的吸附特性和很好的选择性,其识别因子可达4.19。Scatchard分析表明,印迹聚合物微球存在2类不同的结合位点。高结合位点的平衡离解常数Kd1=0.078 mg/L,最大表观结合量Qmax1=53.03 mg/g;低结合位点的离解常数Kd2=0.023 mg/L,最大表观结合量Qmax2=33.95 mg/g。     

胆固醇分子印迹聚合微球的制备及其吸附性能

以胆固醇为模板分子、甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸酯为交联剂,在甲苯-乙腈(9:1, j)混合溶剂中沉淀聚合制备了分子印迹聚合物微球. 采用平衡结合法和Scatchard模型评价了该聚合微球的结合性,考察了其吸附行为. 结果表明,胆固醇分子印迹聚合微球中形成两类不同的结合位点,得到高亲和性结合位点的离解常数和最大表观吸附量分别为0.86 mmol/L和80.4 mmol/g,低亲和性结合位点解离常数和最大表观吸附量分别为0.39 mmol/L和61.6 mmol/g. 此方法合成的分子印迹微球对胆固醇有较好的结合性能,可用于胆固醇的分析检测.     

分子印迹聚合物微球结构与性能的关系

以咖啡因为模板分子,采用单步溶胀聚合法制备了一系列具有不同结构特点的分子印迹聚合物微球(MIPMs),考察了MIPMs结构与吸附及识别性能的关系。结果表明:增大MIPMs的比表面积、在一定范围内提高MIPMs的溶胀率或增大结合点的密度,均可增加MIPMs中可接近性结合点的数量,从而增强MIPMs对咖啡因的吸附与识别能力;提高MIPMs的刚性,可增强印迹孔穴的稳定性,MIPMs的识别能力增强,但吸附能力减弱。研究还从热力学角度分析了MIPMs中不同类型结合点的吸附与识别能力。结果表明,高亲和力结合点比低亲和力结合点具有更强的吸附与识别能力。     

铅离子印迹聚合物微球的制备及其吸附性能研究

以Pb2+为模板,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,十二烷基苯磺酸钠(SDBS)为分散剂,采用乳液悬浮聚合法制备了铅离子印迹聚合物微球。通过静态平衡吸附实验和Scatchard分析法研究了聚合物微球的吸附性能和选择性。结果表明,铅离子印迹聚合微球能有效去除溶液中的铅离子,最大吸附容量为15.29 mg/g。在竞争离子Cd2+存在的溶液中,铅离子印迹聚合物微球呈现出对铅离子的高选择性。Pb2+/Cd2+的识别因子为19.01,结合位点的离解常数Kd=35.61 mg/L,最大表观结合量Qmax=25.19 mg/g。     

沉淀聚合法制备对氨基苯甲酸印迹聚合物及其表征

以对氨基苯甲酸为模板分子,采用沉淀聚合法制备了分子印迹聚合物微球,优化了聚合反应条件,静态平衡吸附实验结果表明,该微球对模板分子存在一种均匀的结合位点,最大表观结合量为49.298μmol/g。应用此微球制备的色谱填充柱能够分离对氨基苯甲酸及其位置异构体邻氨基苯甲酸,分离度为1.42。     

氯霉素分子印迹聚合物合成功能单体筛选及分子识别性能

要获得吸附识别性能良好的非共价型分子印迹聚合物,聚合前模板分子与功能单体间的相互作用情况至关重要。本文以氯霉素（CAP）为模板分子,分别以甲基丙烯酸（MAA）、甲基丙烯酸甲酯（MMA）、丙烯酸（AA）和丙烯酰胺（AM）为功能单体,采用分子动力学计算和紫外光谱法研究单体与模板分子间的相互作用情况以筛选单体,并用实验进行印证。分子动力学计算出结合能ΔE的大小顺序为MAA>AA>AM>MMA;紫外光谱中最大吸收峰红移程度的顺序同样为MAA>AA>AM>MMA,且MAA：CAP=1:4（摩尔比）时两者间已有较强的相互作用。静态吸附法测定由各功能单体合成的CAP分子印迹聚合物微球（MIPMs）的饱和吸附量,结果显示：四种功能单体合成的MIPMs对CAP的吸附性能均明显优于相应非印迹聚合物,不同功能单体所得聚合物的饱和吸附量也有显著差异,其大小顺序同样为MAA>AA>AM>MMA。这一结果与分子动力学计算及紫外光谱分析结果相吻合。最后以MAA为功能单体优化制备MIPMs,扫描电镜表明所得聚合物微球具有良好的单分散性,平均粒径为8.44祄,分散系数为14.2%。用静态平衡结合法对不同CAP与MAA比例合成的MIPMs的吸附识别性能进行研究。实验结果表明所制备MIPMs对CAP的静态分配系数明显高于对结构类似物甲砜霉素（TAP）和氟甲砜霉素（FF）的静态分配系数,具有明显的特异识别性。在CAP:MAA=1:4时,CAP与TAP间的分离因子高达4.57。     

乙酰水杨酸分子印迹聚合物微球的制备及性能研究

以乙酰水杨酸为模板分子,采用沉淀聚合的方式制备了对乙酰水杨酸具有高选择性和亲和性的分子印迹聚合物微球。通过紫外光谱分析法考察了模板分子与功能单体作用规律,优选了功能单体与配合比例。等温吸附实验的结果显示,与相应的空白聚合物相比,印迹聚合物对模板分子具有更高的亲和性;Scatchard数学模型分析的结果表明,印迹聚合物中主要存在一类亲和性质相同的结合位点,其最大表观结合量为37.97 mg/g。选择性吸附实验表明,制备的印迹聚合物对模板分子具有良好的选择性识别能力。     

二步种子溶胀法制备氯霉素分子印迹聚合物微球及其识别性能

以聚苯乙烯乳液为种球、氯霉素为模板分子、甲基丙烯酸为功能单体、二甲基丙烯酸乙二醇酯为交联剂,采用二步种子溶胀法制备了单分散氯霉素分子印迹聚合物微球(MIPMs).通过扫描电镜(SEM),考察了溶胀比、搅拌速度、水油比、交联剂用量、分散荆用量等对MIPMs形态,粒径大小及粒径分布的影响.并用静态吸附实验考察了微球的吸附识...     

利福平分子印迹聚合物的制备及其吸附行为

以利福平为模板分子、甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸酯为交联剂,制备了利福平分子印迹聚合物. 采用平衡结合方法和Scatchard模型评价了该聚合物的结合特性,考察了其吸附行为. 结果表明,利福平分子印迹聚合物中形成了两类不同的结合位点,得到高亲和力结合位点的离解常数和最大表观结合量分别为31.5 mg/mL和23.34 mg/g,低亲和力结合位点的离解常数和最大表观结合量分别为9.22 mg/mL和12.86 mg/g. 实验结果显示,利福平分子印迹聚合物对利福平呈现出了高的选择吸附特性.     

沉淀聚合法制备磺胺二甲嘧啶分子印迹聚合物

以磺胺二甲嘧啶为模板分子,采用沉淀聚合法制备了分子印迹聚合物,并对其选择性和吸附性能进行了研究.等温静态平衡实验结果表明,该印迹聚合物与相应的空白聚合物相比具有高的选择性和亲和性;Scatchard模型分析结果表明,该印迹聚合物对印迹分子存在一种均匀的结合位点,最大表观结合量为31.866 mg/g.     

Characterization and quality assessment of binding properties of the monocrotophos molecularly imprinted microspheres prepared by precipitation polymerization in toluene

To obtain the desired specific adsorbents for monocrotophos (MCP) to enrichment, separation, and analysis of trace pesticides residue in soils and foods, molecularly imprinted polymer microspheres were prepared by precipitation polymerization using MCP, methacylic acid (MAA), ethylene glycol dimethacrylate, azobisisobutyronitrile, and toluene as template, functional monomer, crosslinker, initiator, and porogen, respectively. Computer simulation was employed to demonstrate the mechanism of the interaction between MCP and MAA in toluene. It was found that one MCP was entrapped by two MAAs in toluene through hydrogen bond. The binding properties of MCP in toluene for imprinted microspheres were evaluated by equilibrium rebinding experiments. Scatchard plot analysis revealed that there were two classes of binding sites populated in the imprinted polymer microspheres with dissociation constants of 0.0019 and 0.12 mmol/L, respectively. The specificity of the imprinted microspheres was investigated by binding analysis using MCP and structurally related organophosphorous pesticides. The results indicated that the obtained imprinted microspheres showed a good selectivity for MCP. POLYM. ENG. SCI., 47:1302–1308, 2007. © 2007 Society of Plastics Engineers     

A Novel Molecularly Imprinted Core?CShell Chemiluminescence Sensor: Preparation and Pendimethalin Recognition

Novel molecularly imprinted core?Cshell microspheres were synthesized using hollow silica microspheres as the core. Because of the molecularly imprinted core?Cshell microspheres, the effective binding sites at the surface of the shells were sharply increased; and, the recognition capability for template molecules was greatly improved. Based on this, a novel chemiluminescence sensor was established and successfully applied in the detection of trace pendimethalin in foodstuffs. The proposed sensor exhibited excellent selectivity, good sensitivity and simple operation. High throughput sample detection was realized with satisfactory results.     

表面分子印迹材料制备研究进展

表面分子印迹技术是通过把分子识别位点建立在印迹材料的表面,来提高识别位点与印迹分子的结合速度,进一步加强印迹材料吸附分离效率。从无机硅胶材料和聚合物材料两方面综述了表面分子印迹材料制备技术发展现状,着重评述了表面分子印迹聚合物微球的制备方法及相应产品的性能,并指出表面分子印迹技术存在的不足。     

二氯喹啉酸分子印迹聚合物微球的制备

采用改进的分散聚合方法制得的纳米级聚苯乙烯微球(PS)为种球,以二氯喹啉酸(quinclorac)为模板分子,通过单步溶胀聚合法在水相中制备了单分散分子印迹聚合物微球(MIPs)。通过红外光谱分析MIPs的结合位点;利用紫外光谱研究了MIPs的结合机理和识别特性;用扫描电镜观察了微球的形貌。结果表明,PS微球的粒径分布100～150nm,MIPs的粒径分布为200～300nm;Scatchard分析表明,MIPs在识别二氯喹啉酸过程中存在两类结合位点:高亲和性位点的解离常数KD1=0.0488mmol/L;低亲和性位点的解离常数KD2=0.423mmol/L。     

Preparation and characterization of uniform molecularly imprinted polymer beads for separation of triazine herbicides

Uniform molecularly imprinted polymer beads were synthesized by precipitation polymerization for separation of triazine herbicides. A series of imprinted polymers were prepared using ametryn as template and divinylbenzene as crosslinking monomer, in combination with three different functional monomers under different solvent conditions. Under optimized reaction conditions, we obtained uniform molecularly imprinted polymer microspheres that display favorable molecular binding selectivity for triazine herbicides. The imprinted polymer beads synthesized using methacrylic acid as functional monomer in a mixture of methyl ethyl ketone and heptane showed the best results in terms of particle size distribution and molecular selectivity. Compared with nonimprinted polymer microspheres, the imprinted microspheres displayed significantly higher binding for a group of triazine herbicides including atrazine, simazine, propazine, ametryn, prometryn, and terbutryn. For the first time, precipitation polymerization has been used to produce highly uniform imprinted microspheres suitable for affinity separation of triazine herbicides. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Recognition of 5‐fluorouracil by thermosensitive magnetic surface molecularly imprinted microspheres designed using a computational approach

Thermosensitive magnetic surface molecularly imprinted polymer microspheres based on thermosensitive monomer n ‐isopropylacrylamide (NIPAM) are applied for the recognition of 5‐fluorouracil (5‐FU). A computational analysis is used to predict the interaction sites between 5‐FU and NIPAM, the stoichiometry of the synthesis procedure, and the affinity of imprinted cavities toward 5‐FU. Due to hydrogen bond interactions, a stable complex configuration of 5‐FU and NIPAM shows a binding energy of ?46.50 kJ/mol confirming the suitability of imprinting 5‐FU into thermosensitive polymer network. After optimization, the appropriate stoichiometry of 5‐FU to NIPAM is set to 1:4 during the preparation process. The simulated imprinted cavities show affinity toward 5‐FU, with a binding energy of ?112.24 kJ/mol. A preliminary experimental evaluation for the drug recognition of thermosensitive magnetic surface molecularly imprinted polymer microspheres is made, obtaining an adsorption capacity of 21.72 mg/g at 25 °C. Pseudo‐second‐order kinetics well describes the adsorption process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45468.     

喹唑啉分子印迹聚合物微球的吸附特性

以2,4-二氯-6,7-二甲氧基喹唑啉(DCQAL)为模板分子,采用单步溶胀聚合法制备了粒径均匀的分子印迹聚合物微球(M IPM s),并用静态吸附法研究了功能单体、三乙胺及水对M IPM s吸附性能的影响,考察了微球的识别性能。制得的M IPM s主要靠氢键作用吸附与识别模板分子,甲基丙烯酸(MAA)与模板分子间能产生较强的氢键作用,以其为功能单体制得的M IPM s具有较好的吸附与识别性能,其高亲和力与低亲和力结合点的最大表观吸附量分别为17.53μmol/g和117.02μmol/g,以4-氯-6,7-二甲氧基喹唑啉(CQAL)为竞争底物,其分离因子α达1.78。往吸附液中添加三乙胺或少量水会减弱M IPM s的吸附能力。