球形印迹交联壳聚糖聚合物的制备及其对尿素的吸附性能研究

采用乳液聚合法制备了球形尿素-壳聚糖分子印迹聚合物。通过正交试验优化了印迹聚合物的制备条件:在乙酸体积分数为2%,戊二醛用量为1 mL,转速为900 r/min,模板分子用量为3 g的条件下制备的印迹聚合物对尿素的吸附量为7.16 mg/g,非印迹聚合物对尿素的吸附量为3.84 mg/g。聚合物的红外图谱研究表明,戊二醛参与了交联反应且模板分子尿素被印迹在聚合物上,聚合物经洗脱后模板分子被基本除去。分子印迹聚合物表面具有均一选择性的吸附位点,最大表观吸附量为9.69 mg/g。     

对羟基苯甲酸乙酯印迹聚合物固相微萃取制备及条件优化

采用分子印迹技术,以对羟基苯甲酸乙酯(模板分子):α-甲基丙烯酸(功能单体):乙二醇二甲基丙烯酸酯(交联剂)摩尔比为1∶4∶20,反应温度为80℃,反应时间为15h,本体聚合的方法合成印迹聚合物。利用微量进样器和玻璃毛细管自制分子印迹固相微萃取装置。将自制固相微萃取与气相色谱联用,并对萃取头的萃取条件如萃取温度、萃取时间、解析时间、溶液离子强度等进行优化。通过选择性吸附实验测得,分子印迹固相微萃取对对羟基苯甲酸甲酯、对羟基苯甲酸乙酯和对羟基苯甲酸丙酯的萃取量分别为103.54、134.26和114.68μg,均大于非分子印迹固相微萃取的萃取量47.88、49.24和41.41μg,印迹萃取头表现出了良好的吸附性和选择性。     

三唑醇分子印迹整体柱用于结构类似物的分离与分析

以农药三唑醇为模板分子,采用热引发原位聚合法制备了具有特定识别性能和分离能力的分子印迹聚合物(MIP),并用作高效液相色谱固定相,实现了模板分子与其结构类似物的分离,三唑醇MIP整体柱(50mm×4.6mm,i.d.),采用甲醇-水(体积比为3∶7)为流动相,流速为1.0mL/min。制备的分子印迹整体聚合固定相对模板分子在含水流动相中与其类似物有良好的选择性。     

红霉素分子印迹聚合物纳米微球的制备及其吸附特性

以红霉素为模板分子、甲基丙烯酸为功能单体、乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法制备了粒径均一的红霉素纳米分子印迹聚合物微球,优化了分子印迹聚合物的合成条件,确定了模板分子与功能单体的最佳摩尔比为1:3,对其进行了表征. 结果表明,所制聚合物对红霉素的实际最大吸附量可达202.12 mg/g,吸附约200 min达到平衡,对红霉素具有良好的选择性吸附能力.     

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。     

三聚氰胺分子印迹固相萃取小柱的研制及其应用

用本体聚合法制备三聚氰胺分子印迹聚合物,通过静态平衡吸附实验及固相萃取实验表征其固相萃取性能,结合HPLC法对实际奶粉样品中的三聚氰胺进行测定.三聚氰胺模板聚合物的吸附能力强于空白聚合物;固相萃取柱对三聚氰胺标准溶液(0.3 mmoL/L)一次性萃取率达97.01%,奶粉样品中三聚氰胺测定的平均回收率为101.2%.印...     

分子印迹杂化材料的溶胶-凝胶法制备及选择性固相萃取牛奶中洛美沙星

以兽药洛美沙星为模板分子,3-氨基丙基三乙氧基硅烷为功能单体,甲基三甲氧基硅烷为交联剂,采用溶胶-凝胶分子印迹技术,以离子对及疏水作用方式,在水相体系中合成了具有分子识别作用的的新型有机-无机杂化分子印迹聚合物。静态吸附和Scatchard分析实验结果表明,此印迹材料对洛美沙星的结合存在两个结合位点,最大吸附容量分别为95.65与127.45μmol/g。以此印迹材料作为固相萃取剂,优化萃取条件,成功应用于牛奶中洛美沙星测定。     

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.     

水相中马尿酸分子印迹聚合物的制备及其性能研究

采用分子印迹技术,以马尿酸为模板分子,在水相中制备其印迹聚合物。用于液相色谱固定相,结果表明,该聚合物固定相表现出良好的分离选择性,能够使马尿酸与和其结构相似的苯甲酸及咖啡酸快速基线分离。并通过平衡吸附法分析了印迹聚合物的识别特性,结果表明分子印迹聚合物对马尿酸有特异性吸附。     

分子印迹微溶胶的制备及对水中2,4-二氯苯酚的吸附研究

以2,4-二氯苯酚(2,4-DCP)为模板分子,甲基丙烯酰胺为功能单体,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微溶胶(MIPM)。采用紫外光谱法(UV)研究模板与单体间的结合作用,扫描电子显微镜(SEM)表征印迹聚合物的表面形貌。通过平衡吸附试验对MIPM的吸附性能进行评价。结果表明,当以乙腈作为致孔剂,功能单体与模板分子的摩尔比为4:1时,MIPM对2,4-DCP的印迹因子为1.93,最大吸附容量为159.61 mg/g,吸附在150 min左右可达到平衡。将MIPM用作固相萃取(SPE)柱填料,对水样中的2,4-DCP进行富集试验,回收率为96.30%~108.66%。     

Molecularly Imprinted Polymer for Solid-Phase Extraction of Phenolic Acids from Salicornia herbacea L.

This paper reports the application of a molecularly imprinted polymer (MIP) for the extraction and separation of phenolic acids from Salicornia herbacea L. (S. herbacea) using a solid phase extraction (SPE) system. The template of the MIP for phenolic acid extraction and separation was selected experimentally as one of seven templates. The obtained material with Benzoic acid (BA) as a template had the best extraction capacity of phenolic acids from S. herbacea. Water and methanol/HCl were selected as a washing solvent and elution solvent, respectively. The good linearity was obtained for the three targets, ranging from 10 to 500 μg mL^?1 (R² > 0.999), with relative standard deviations ≤ 5.0%. Overall, the proposed method using MIPs is expected to have a wide range of applications.     

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).     

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。     

用于蛋白质BSA识别的温度/pH双敏印迹聚合物

用N-异丙基丙烯酰胺(NIPAM)和壳聚糖为功能单体,牛血清白蛋白（BSA）为模板蛋白,在改性SiO₂表面制备温度/pH双敏蛋白质印迹聚合物。TEM、FTIR和TG等结果证明印迹层已成功接枝在载体表面。系统研究了聚合物的温度/pH双敏性、吸附容量、吸附动力学、特异性、竞争吸附性及重复性。结果表明,印迹聚合物（MIP）的溶胀率和吸附容量受温度和pH影响较大,高温碱性收缩,低温酸性溶胀。在pH 4.6和35℃下,对0.6mg/mL BSA吸附4h时获得较大的吸附容量（83.74mg/g）,印迹因子为2.02。同时MIP也有较好的特异性和竞争吸附性。重复5次后,吸附容量仍能维持在88%,说明重复性良好。这种新型的温度/pH双敏蛋白质分子印迹合成方法简单,在蛋白质的分离和识别方面有较好的应用前景。     

Grafting of molecularly imprinted polymers from the surface of Fe3O4 nanoparticles containing double bond via suspension polymerization in aqueous environment: A selective sorbent for theophylline

Molecularly imprinted polymers (MIPs) were grafted from the surface of Fe₃O₄ nanoparticles containing double bond via suspension polymerization in aqueous environment, and the leakage of Fe₃O₄ nanoparticles from MIPs was overcome in this study. The effect of different cross‐linker on adsorption capacity of the resultant magnetic MIPs was investigated using pure trimethylolpropane trimethacrylate (TRIM) or the mixture of TRIM and divinylbenzene (DVB) as cross‐linker. Both magnetic MIPs exhibited higher adsorption capacity for the template theophylline than the corresponding non‐imprinted polymer, and Freundlich model fitted reasonably well for theophylline adsorption on both magnetic MIPs. In addition, both magnetic MIPs exhibited good recognition properties for the template theophylline versus caffeine, and the selectivity of magnetic MIPs using pure TRIM as cross‐linker (mag‐MIP‐TRIM) was much higher than those using the mixture of TRIM and DVB as cross‐linker (mag‐MIP‐TRIM and DVB). The adsorption dynamics of theophylline on both magnetic MIPs fitted well with the first‐order kinetic model, but the adsorption equilibrium on mag‐MIP‐TRIM and DVB reached faster than that on mag‐MIP‐TRIM. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Molecular imprinted solid‐phase extraction of huperzine A from Huperzia Serrata

On the basis of the non‐covalent interaction between template and monomer, porous molecularly imprinted polymers (MIPs) were synthesized by a thermal‐initiated polymerization method using huperzine A as template, acrylamide, or methacrylic acid as function monomer, ethylene glycol dimethacrylate as cross‐linking agent. The interaction between template and functional monomers was studied by UV spectrophotometry, which showed a formation of huperzine A‐monomer complexes with stoichiometric ratio of 1 : 2 in the pre‐polymerized systems. The resultant MIP particles were tested in the equilibrium binding experiment to analyze their adsorption ability to huperzine A, and were characterized by Fourier Transform Infrared (FTIR) study. The recognition properties of MIP were estimated in solid‐phase extraction by selecting four compounds (isolated from the Chinese herb Huperzia serrata) as substrates, and were compared with and prior to those of the NIP. High affinity and adsorption of MIP1 which was prepared in chloroform with huperzine A as imprinted molecule, and acrylamide (AM) as functional monomer, made an attractive application of MIP1 in separation processes. In final, using MIP1 solid‐phase extraction micro‐column, huperzine A was enriched and separated from the real extraction sample of Huperzia serrata. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

戊唑醇-三唑酮双模板分子印迹聚合物在烟叶农残检测中的应用

以戊唑醇（TBZ）和三唑酮（TDF）为双模板分子，甲基丙烯酸（MAA）为功能单体，乙二醇二甲基丙烯酸酯（EGDMA）为交联剂，按摩尔比为1∶4∶20制备了戊唑醇-三唑酮双模板分子印迹聚合物（MIPs）。考察了MIPs的吸附动力学、静态吸附及亲和位点特征和选择识别性能。结果表明，MIPs可在2.5h内达到吸附平衡，Scatchard分析得出MIPs存在高低两类亲和位点，且具有良好的组选择性和特异选择性。以MIPs作为固相萃取填料，制备分子印迹固相萃取柱（MISPE）用于烟叶样品前处理，并建立MISPE-超高效液相色谱-串联质谱法检测烟叶中（戊唑醇、三唑酮、腈菌唑和三唑醇）残留的方法。结果显示，MISPE柱对戊唑醇、三唑酮、腈菌唑和三唑醇的富集效果较好，平均回收率为72%~110.3%，相对标准偏差在2.38%~7.92%（n=3）。该方法简单、选择性高，可实现对烟叶中三唑类杀菌剂残留的准确分析。     

壳聚糖印迹聚合物对Zn2+的吸附动力学

以Zn²⁺作为模板,加入分散剂石蜡、预交联剂甲醛、交联剂环氧氯丙烷,制得特性壳聚糖印迹聚合物,用X射线衍射仪表征了聚合物的结构,考察了聚合物用量、温度等对吸附Zn²⁺的影响,研究了印迹聚合物对Zn²⁺的吸附动力学、等温吸附特性。结果表明,印迹聚合物合成过程中打破了壳聚糖原有晶体的规整性,增加了大量的配位基团,使聚合物的吸附容量大大增加,同时聚合物对Zn²⁺有很好的选择吸附性,对Zn²⁺、Cd²⁺、Mg²⁺、Mn²⁺溶液的分离因子均大于1.5;印迹聚合物能快速吸附溶液中Zn²⁺,整个吸附过程符合拟二级动力学模型：t/Q_t=8.1744+2.0186t,相关系数为0.998,吸附平衡容量模型计算值与实验值较为吻合;印迹聚合物对Zn²⁺的等温吸附过程符合Langmuir吸附等温吸附模型：C_e/Q_e=1.3297+0.02701C_e,最大吸附容量为37.023 mmol/g,吸附过程主要以单分子层的吸附形式进行。     

Molecularly imprinted polymers for the selective recognition of l‐phenylalanine based on 1‐buty‐3‐methylimidazolium ionic liquid

To enhance the affinity of 4‐vinyl pyridine to l ‐phenylalanine (l ‐Phe) and convert the imprinting process from the aqueous phase to the organic phase, an oil‐soluble amino acid ionic liquid was introduced as a template. In this study, 1‐butyl‐3‐methylimidazolium α‐aminohydrocinnamic acid salt was first applied to prepared surface molecularly imprinted polymers (MIPs) in acetonitrile for the selective recognition of l ‐Phe. Fluorescence quenching analysis of the functional monomer on the template was investigated under different conditions to study the imprinting mechanism. Several binding studies, such as the sorption kinetics, sorption thermodynamics, and solid‐phase extraction application, and the chiral resolution of racemic phenylalanine were investigated. The binding isotherms were fitted by nonlinear regression to the Freundlich model to investigate the recognition mechanism. The affinity distribution analysis revealed that polymers imprinted by ionic liquid showed higher homogeneous binding sites than those imprinted by l ‐Phe. The competition tests were conducted by a molecularly imprinting solid‐phase extraction procedure to estimate the selective separation properties of the MIPs for l ‐Phe. The target MIP was shown to be successfully for the separation of l ‐Phe from an amino acid mixture. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42485.