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。     

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...     

Zn2+配位双模板印迹聚合物的制备表征及同时萃取升麻中的阿魏酸和咖啡酸

以Zn²⁺-阿魏酸-咖啡酸配合物为模板制备了双分子印迹聚合物,优化了制备条件,用傅里叶红外光谱和扫描电镜对分子印迹聚合物进行结构表征,测试了分子印迹聚合物的吸附特性,探讨了分子印迹聚合物固相萃取应用效能并对萃取条件进行了优化.结果表明,当预反应混合液中金属离子、模板总量(阿魏酸-咖啡酸摩尔比为2:3)、功能单体及交联剂用量比为1:1:3:30(摩尔比)时,所得印迹聚合物对两种模板(阿魏酸和咖啡酸)均具有最好的吸附性能,吸附量分别达51.12mg/g和70.26mg/g.吸附动力学测试表明吸附3h,分子印迹聚合物可达到吸附平衡.用分子印迹聚合物进行固相萃取时,优化的淋洗过程为1.00mL H₂O、1.00mL甲醇-H₂O (3/7,体积比)及1.00mL甲醇-H₂O-ACN (4/4/2,体积比),洗脱溶剂为2.00mL甲醇.在优化条件下,分子印迹聚合物可同时选择富集升麻初提液中的阿魏酸和咖啡酸,二者回收率分别为92.67%和95.42%,而且产品中杂质少于用硅胶萃取所得产品.     

基于对巯基苯胺膜的高灵敏己烯雌酚印迹传感器的制备及应用

通过自组装技术，分别以金硫键（Au—S）和氢键在羧基化多壁碳纳米管（CMWCNTs）和纳米金（AuNPs）修饰的电极表面成功组装功能单体对巯基苯胺（p-ATP）和模板分子己烯雌酚（DES），在含有p-ATP、DES、氯金酸和电聚合介质四丁基高氯酸铵的聚合液中采用电聚合的方法在组装电极表面形成聚合物膜，并用50%乙醇-0.1mol/L硫酸水溶液（1∶1，体积比）洗脱模板分子，成功制备了用于检测己烯雌酚的分子印迹电化学传感器。采用循环伏安法和差分脉冲伏安法研究印迹传感器的印迹效果和分析性能，并将该传感器应用于食品中己烯雌酚的快速检测。在最佳条件下，己烯雌酚的线性范围为1.0×10^-9～1.0×10^-5mol/L，检出限为3.3×10^-10mol/L，样品加标平均回收率为83.46%～98.21%，相对标准偏差（RSD）在1.01%～3.74%之间（n=5）。该传感器操作简单、检测快速灵敏、成本低、抗干扰能力强、稳定性好，有重要的应用价值。     

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。     

分子印迹技术与固相微萃取技术的联用

固相微萃取是一项新颖的样品前处理技术,分子印迹技术是一种制备具有分子识别能力材料的新兴技术。将两项技术相联用,即将分子印迹聚合物作为固相微萃取的涂层材料,具有良好的应用前景。它既具有固相微萃取高效萃取的优点,又具有分子印迹聚合物所具有的强大的分子识别能力。综述了分子印迹技术与固相微萃取技术相联用的研究进展。     

分子印迹水凝胶固相萃取石油有机硫组分

以壳聚糖为功能单体,制备苯并噻吩类硫组分分子印迹固相萃取剂,系统地研究了其分子识别机理,根据目标分子的结构理性地选择了交联剂、致孔剂和聚合方法,探索了不同制备条件对模板聚合物特异性识别能力的影响;总结了影响印迹聚合物识别能力的一般规律,试验结果显示,以环氧氯丙烷为交联剂制备得到的印迹材料对二苯并噻吩的吸附容量达到17.53 mg/g。     

双模板分子印迹聚合物在奶粉检验中的应用研究

采用本体聚合法制备三聚氰胺(MEL)与双氰胺(DCD)双模板分子印迹聚合物(MEL/DCD-MIPs),将其作为固相萃取介质,实现了奶粉中MEL与DCD富集与纯化,建立了奶粉中两种物质同时检测的方法。通过热力学、选择性和动态结合试验表明,与单模板分子印迹聚合物相比,双模板分子印迹聚合物由于双模板-功能单体分子间的多位点协同作用而有更好的印迹效应,对MEL和DCD结合能力高于结构类似物三聚氰酸(CYA)。固相萃取试验显示,MEL/DCD-MIPs可以从市售奶粉中选择性地分离、富集MEL与DCD,对MEL与DCD的加样回收率分别为93.1%~100.1%和75.7%~82.5%,RSD均小于5.2%。所制得的MEL/DCD-MIPs可应用于奶粉等食品中氰胺类物质的检测。     

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。     

木犀草素分子印迹聚合物的分子识别特性及固相萃取研究

采用分子印迹技术,以木犀草素为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,通过热引发聚合,制备了木犀草素分子印迹聚合物,并通过装入固相萃取柱研究了聚合物对木犀草素的选择性能.结果表明,该分子印迹聚合物对模板分子具有高度选择性和识别能力,而空白聚合物却不具备这样的特性.将木犀草素分子印迹聚合物用于固相萃取花生壳提取物,分离富集其中的木犀草素活性成分,在萃取柱上载样品之后,先用V(乙醇):V(水)=1:1溶液进行清洗,再用V(乙醇):V(水)=7:5溶液进行目标分子的洗脱,木犀草素的纯度可由1.6%提高到94.1%,回收率90.0%.木犀草索分子印迹固相萃取柱具有较好的稳定性和耐用性能,使用4次后其选择识别性能仍未降低,显示该聚合物具有直接作为复杂天然产物中木犀草素分离提取材料的潜能.     

四溴双酚A分子印迹聚合物的制备及其吸附机制初探

采用分子印迹技术,以四溴双酚A为模板分子、2-乙烯吡啶为功能单体、乙二醇二甲基丙烯酸酯为交联剂。通过本体聚合法合成了对四溴双酚A具有高度选择性的印迹聚合物。平衡吸附实脸表明：与空白聚合物相比,四溴双酚A印迹聚合物具有较高的吸附能力和选择识别能力。同时比较了印迹聚合物对模板分子和结构相似物的识别能力。结果表明印迹聚合物对四溴双酚A具有更好的特异选择性和识别能力,为复杂介质中四溴双酚A的富集检测提供了一种快速准确有效的方法。     

Computer simulation and preparation of molecularly imprinted polymer membranes with chlorogenic acid as template

A computational approach was developed for screening functional monomers for rational design of molecularly imprinted polymer (MIP) membranes. It was based on a comparison of the binding energy of complexes between a template and various functional monomers. According to the results of theoretical calculations, MIP membranes with chlorogenic acid as a template were prepared with a UV irradiation polymerization method, using 4‐vinylpyridine as a functional monomer and N,N′‐methylenebisacrylamide as a crosslinker, with poly(vinylidene fluoride) microfiltration membranes as the support. Membranes covered with a thin layer of imprinted polymer selective to chlorogenic acid were then obtained and tested using the equilibrium‐adsorption method. The high affinity of these synthetic membranes to chlorogenic acid, together with their straightforward and inexpensive preparation, provides a good basis for the development of applications of imprinted polymers in separation processes such as solid‐phase extraction. Copyright © 2011 Society of Chemical Industry     

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     

单体对分子印迹聚合物分子识别能力的影响：量子化学计算与实验研究

采用密度泛函方法计算功能单体与印迹分子的结合能,以与目标分子结合能最大的单体分子来合成分子印迹聚合物.为此,以茶碱为印迹分子,氯仿为溶剂,首先计算了茶碱与甲基丙烯酸、丙烯酰胺和三氟甲基丙烯酸的结合能,其强度顺序为：三氟甲基丙烯酸 > 甲基丙烯酸 > 丙烯酰胺.然后以茶碱为印迹分子、氯仿为溶剂、二甲基丙烯酸乙二醇酯为交联剂,分别采用上述3种单体合成分子印迹聚合物并测定了其分子识别能力,实验结果和量子化学计算结果具有一致性.最后,采用1H NMR考察了茶碱和上述3种单体之间的氢键作用,揭示出二者相互作用的内在机制.研究结果表明量子计算方法可以应用于合成分子印迹聚合物时单体的选择.     

印迹水凝胶作为氟尿嘧啶载体的药物缓释性能

以氟尿嘧啶为模板药物,以甲基丙烯酸羟乙酯为骨架单体,以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂合成印迹水凝胶,并通过扫描电镜、红外光谱及差示热量扫描等测试手段对凝胶进行了表征,结果表明：制备的印迹水凝胶表面无孔、光滑,氟尿嘧啶与其中的单体通过氢键结合成了复合物,同时经处理后凝胶中已不再残留未反应的单体。印迹水凝胶的吸水溶胀性能实验结果显示其吸水溶胀性能随制备中模板药物的含量的增加而增强,同时同一凝胶的溶胀速度与溶胀率随体系pH值的升高而增强。在氟尿嘧啶溶液中测定水凝胶的药物负载量,结果显示：印迹水凝胶的药物负载能力明显强于非印迹水凝胶,同时印迹水凝胶（8∶1）对药物的负载能力强于印迹水凝胶（4∶1）,药物负载量高达0.0914 mg/g。在模拟体液中测试水凝胶对药物的释放效果结果显示：印迹水凝胶对药物的缓释作用明显优于非印迹水凝胶,并且印迹水凝胶（8∶1）对药物的缓释效果优于印迹水凝胶（4∶1）,对药物的释放平缓,同时,释放体系pH值的升高不利于印迹水凝胶的药物缓释效果。     

以混旋的头孢拉定为模板的分子印迹聚合物的制备及拆分性能研究

以混旋的头孢拉定为模板分子与合成的（S）-（1-苯乙基）-甲基丙烯酰胺作为功能单体制备分子印迹聚合物,并用高效液相色谱法对印迹聚合物的选择性进行了考察。实现了对混旋的头孢拉定的拆分。同样的方法分别制备了3种混旋的氨基酸衍生物的分子印迹聚合物,未能实现对其混旋物质的分离。对比得出结论：对混旋物质的直接印迹需要模板分子应具有4个以上的作用位点。     

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。     

Preparation and application of sulfadiazine surface molecularly imprinted polymers with temperature‐responsive properties

Novel, temperature‐responsive molecularly imprinted polymers (TMIPs) based on potassium hexatitanate whiskers for selectively adsorbing sulfadiazine (SDZ) from aqueous media were prepared with methacrylic acid (MAA) and 4‐vinylpyridine (4‐VP) as cofunctional monomers and N‐isopropyl acrylamide (NIPAM) as a temperature‐responsive monomer. The template–monomer interactions were studied by molecular simulation. In particular, the effects of different kinds of crosslinkers on the selective recognition ability of the TMIPs in water media were investigated. The temperature–responsive adsorption performance and phase behavior of the molecularly imprinted polymers were studied by batch‐mode binding experiments, swelling experiments, and contact angle testing. The results demonstrate that the combination of MAA, 4‐VP, and NIPAM was a favorable temperature‐responsive imprinted system for SDZ in water, and the cocrosslinking agent of ethylene glycol dimethacrylate (EGDMA) and N,N′‐methylene bisacrylamide (MBA) was more suitable compared with either pure EGDMA or MBA. The adsorption kinetics and adsorption isotherms were analyzed by the fitting of different adsorption models. Also, the effect of the temperature on the recovery was investigated by the determination of the spiked SDZ in real‐water samples with solid‐phase extraction and high‐performance liquid chromatography. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41769.     

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