替代模板法制备甲硝唑分子印迹聚合物及其在血清样品固相萃取中的应用

以甲硝唑酯化物(MNZ-Es)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,氯仿为致孔剂,合成了对甲硝唑(MNZ)具有特异吸附性能的分子印迹聚合物(MIP).由静态吸附实验结果得知,印迹指数为2.02,说明MIP对MNZ具有良好的识别性能.MIP吸附属于Langmuir吸附模型,其对MNZ的吸附属于单...     

赤霉酸分子印迹聚合物及印迹膜的制备与性能研究

以赤霉酸(GA3)为印迹分子,改变功能单体与致孔剂种类合成了四个分子印迹聚合物(MIP1-4)及两个分子印迹膜(MIM1-2).采用紫外光度法分别测定了印迹分子分别与功能单体丙烯酰胺(AM)和甲基丙烯酸(MAA)间的结合常数和化学计量比(n＝2).平衡结合实验研究表明,以AM为单体制备的MIP1对印迹分子GA3具有更高的结合量和良好的印迹效率.膜渗透及膜过滤实验表明,以AM为单体制备的MIM1对GA3分子具有一定的选择性分离性能.     

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。     

分子印迹技术制备石油有机硫组分固相萃取剂的研究

用分子印迹技术合成了对石油有机硫组分二苯并噻吩(Dibenzothiophene，DBT)具有高效选择性的分子模板聚合物(Molecularly Imprinted Polymer，MIP)，通过静态吸附的方法研究了不同功能单体和致孔剂及其用量对模板聚合物特异性识别能力的影响．实验表明，以4-乙烯基吡啶(4-VP)为功能单体，在甲苯溶剂中聚合得到的固相萃取剂对DBT具有较大的吸附富集能力和识别特性．其饱和吸附容量达到48．3mg／g．     

以局部结构类似物为类模板的分子印迹整体柱在线检测三甲氧苄啶

以三聚氰胺(MAM)为类模板分子,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,聚己二醇(PEG400)为致孔剂,原位聚合法制备了对三甲氧苄啶(TMP)有较强选择性吸附作用的分子印迹(MIP)整体柱.以该MIP整体柱为高效液相色谱柱,考察了其在不同色谱流动相组成条件下对TMP的识别性能.结果显示,MIP整体柱在甲醇、乙腈、水等条件下能够吸附TMP而不出峰.可以利用MIP整体.柱在甲醇-水( 80:20,V/V)中在线选择性吸附(或富集)TMP,然后将流动相转换为甲醇进一步除去疏水性杂质,最后用强洗脱剂洗脱TMP出峰.MIP整体柱线检测人血清中TMP的工作曲线为A=42.8c 3.03(r=0.9994);线性范围为8.3～93.8 mg/L;检出限为0.14 mg/L.     

季戊四醇三丙烯酸酯-丙烯酸丁酯共聚微球的合成及孔结构特性研究

以季戊四醇三丙烯酸酯、丙烯酸丁酯为共聚单体,乙酸丁酯为致孔剂,用悬浮聚合法合成了-系列不同表面结构的共聚微球.使用扫描电镜、BET氮气吸附,傅立叶红外光谱等分析手段,对微球进行了结构测定,并研究了单体与致孔剂比例、两种单体比例及不同致孔剂对于聚合物孔结构的影响.经过合成条件的筛选,得到了平均孔径为100nm左右的球形聚合物.     

士的宁分子印迹整体柱的制备

以士的宁为模板分子，甲基丙烯酸为功能单体，乙二醇二甲基丙烯酸酯作为交联剂，甲苯和十二醇混合溶液为致孔剂，用原位分子印迹技术，合成了士的宁分子印迹整体柱。通过优化合成条件，结果显示：模板分子、功能单体与交联剂之间的比例以1：4：16最佳，致孔剂中甲苯的最佳含量为18％（V/V)；对士的宁整体柱的色谱条件包括流动相组成、流速、柱温等进行了考察，并用于士的宁和马钱子碱的分离，其分离因子为3．5。     

柚皮苷分子印迹膜的水相制备与识别

以柚皮苷为印迹分子,PEG为致孔剂,在水相中制备了柚皮苷分子印迹壳聚糖膜.分别讨论了交联剂、致孔剂和印迹分子的用量对印迹膜结构和性能的影响.用SEM观察了致孔剂对印迹膜形貌及孔径的影响.紫外吸收光谱分析、柚皮苷在不同体系中的溶解度变化,以及红外光谱分析的结果表明功能聚合物壳聚糖和模板分子柚皮苷间形成了氢键.膜的渗透实验结果表明,在水相中,柚皮苷分子印迹膜能有效地从新橙皮苷和柚皮苷的混合液中分离出印迹分子柚皮苷,选择透过率为11.16%.     

3-吲哚乙酸印迹聚合物的制备及其分子识别性能

以IAA为模板分子,4-乙烯基吡啶(4-Vpy)为功能单体,乙腈为致孔剂,采用本体聚合方法,制备了IAA的印迹聚合物P(4-Vpy),用色谱法评价了其分子识别性能,并且与同样条件下以丙烯酰胺(AA)为功能单体合成的IAA印迹聚合物P(AA)进行了比较。结果表明,乙腈为流动相时,P(4-Vpy)比P(AA)对IAA具有更高的印迹效率,对IAA表现出了更好的分子识别能力。流动相对P(4-Vpy)分子识别能力的影响实验证明,静电作用在其分子识别过程中起重要作用。两种不同用量的乙腈为致孔剂制备所得IAA印迹聚合物P(4-Vpy)和P`(4-Vpy)的色谱测定结果表明,致孔剂的加入量对其印迹效率有显著影响。     

大黄素分子印迹整体柱的合成及性能表征

以大黄素分子为模板,甲基丙烯酸为单体,乙二醇二甲基丙烯酸酯为交联剂,甲苯和十二醇为混合致孔剂,用原位聚合法合成了一系列分子印迹整体柱,并考察了模板分子在不同条件下合成的印迹聚合物及参考聚合物上保留因子的变化规律.在优化的合成条件下制得的分子印迹整体柱能有效地分离大黄素及其类似物.对分子印迹聚合物及参比聚合物的孔度分析数据表明:分子印迹聚合物中具有两种不同的孔度分布,而参比聚合物中只有一种.     

Molecularly Imprinted Polymer Monolithic Column Separation of Isomers and Analogues of Vanillin by Capillary Electrochromatography

A vanillin imprinted capillary monolithic column was synthesized by in situ polymerization reaction using ethylene-glycol dimethacrylate as cross-linking monomer and methacrylic acid as functional monomer. Under the optimum conditions of capillary electrochromatography, this molecularly imprinted polymer （MIP）-based column showed high selectivity and could recognize not only template molecule vanillin but also positional isomer o-vanillin from their structural analogues.     

Combination of computational methods,adsorption isotherms and selectivity tests for the conception of a mixed non-covalent–semi-covalent molecularly imprinted polymer of vanillin

A novel molecularly imprinted polymer (MIP) for vanillin was prepared by photo initiated polymerization in dichloromethane using a mixed semi-covalent and non-covalent imprinting strategy. Taking polymerisable syringaldehyde as “dummy” template, acrylamide was chosen as functional monomer on B3LYP/6-31+G(d,p) density functional theory computational method basis with counterpoise. The binding parameters for the recognition of vanillin on imprinted polymers were studied with three different isotherm models (Langmuir, bi-Langmuir and Langmuir–Freundlich) and compared. The results indicate an heterogeneity of binding sites. It was found and proved by DFT calculations that the specific binding of vanillin in the cavities is due to non-covalent interactions of the template with the hydroxyphenyl- and the amide-moieties. The binding geometry of vanillin in the MIP cavity was also modelled. The obtained MIP is highly specific for vanillin (with an imprinting factor of 7.4) and was successfully applied to the extraction of vanillin from vanilla pods, red wine spike with vanillin, natural and artificial vanilla sugar with a recovery of 80%.     

Supported liquid membrane-modified piezoelectric flow sensor with molecularly imprinted polymer for the determination of vanillin in food samples

An on-line supported liquid membrane-piezoelectric detection system, based on a molecularly imprinted polymer (SLM-QCM-MIP) manifold, has been developed and applied to the quantitative determination of vanillin in food samples. The analyte is extracted from a donor phase into the hydrophobic membrane, and then back extracted into a second aqueous phase used as the acceptor solution. The quantification of vanillin was performed using a quartz crystal microbalance modified with a molecularly imprinted polymer (MIP). The method shows a linear range between 5 and 65 μM, with a relative standard deviation of ±4.8% (at 5 μM). The method was validated by analysing food samples and comparing the results with an SLM based on spectrophotometric quantification.     

粉煤灰基氧氟沙星分子印迹聚合物的制备及其应用

以工业废料粉煤灰微球为基质,氧氟沙星 (OFL) 为模板分子,采用表面印迹法制备印迹材料MIP。通过紫外光谱法结合理论分析选择实验条件,并对该印迹材料结构、吸附行为进行研究。结果表明,该印迹材料对氧氟沙星具有良好的特异识别性和优良的亲和性。与以硅胶为载体制备的印迹聚合物相比,该材料吸附容量更高和印迹效果更好。将其作为固相萃取填料对鸡产品进行分离富集,与C18柱相比,分离富集效果更好。结合UPLC,对实际样品中氧氟沙星进行分析,回收率为82.0%-96.7%,相对标准偏差低于5.5%,可用于鸡产品中氧氟沙星分离分析。     

硅胶表面替米考星分子印迹聚合物的制备

表面印迹接枝技术即在硅胶表面或有机聚合物载体表面[1]、毛细管表面[2]进行接枝聚合并引进分子印迹的技术[3-6]。替米考星(Tilm icosin)是一种由泰乐菌素半合成的大环内脂类畜禽专用抗生素。本文以替米考星为模板分子,以甲苯为溶剂,以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸     

Synthesis of molecularly imprinted polymer with 7-chloroethyl-theophylline-immobilized silica gel as template and its molecular recognition function

By reaction of 7-chloroethyl-theophylline with aminopropylsilanized silica gel we synthesized a 7-chloroethyl-theophylline-immobilized silica gel as template molecule and prepared a molecularly imprinted polymer (MIP-Si), which had special recognition sites to 7-chloroethyl-theophylline. A conventional molecularly imprinted polymer (MIP) using 7-chloroethyl-theophylline as template was also prepared for comparison. Binding abilities to 7-chloroethyl-theophylline and its structural analogs revealed that the MIP-Si shows much higher binding speed and much more binding capacity than the MIP does.     

反乌头酸分子印迹聚合物微球的制备及其分子识别功能

以乙腈为分散剂,采用沉淀聚合法合成了反乌头酸分子印迹聚合物微球。研究了合成反应条件对聚合物形貌的影响,发现聚合前主客体氢键络合物和功能单体氢键低聚体是控制微球形成及其粒径大小的关键因素。通过振荡吸附法对聚合物的结合特性进行了评价,发现印迹聚合物微球对模板分子的识别选择性优于块状印迹聚合物和非印迹聚合物。     

Iodinated molecularly imprinted polymer for room temperature phosphorescence optosensing of fluoranthene

A novel molecularly imprinted polymer (MIP) of high interest for room temperature phosphorescence (RTP) sensing systems is described; the synthesized MIP contains iodine as internal heavy atom in the polymeric structure and its applicability for RTP sensing of fluoranthene at microg L(-1) levels is demonstrated.     

Molecularly imprinted polymers: An analytical tool for the determination of benzimidazole compounds in water samples

Molecularly imprinted polymers (MIPs) for benzimidazole compounds have been synthesized by precipitation polymerization using thiabendazole (TBZ) as template, methacrylic acid as functional monomer, ethyleneglycol dimethacrylate (EDMA) and divinylbenzene (DVB) as cross-linkers and a mixture of acetonitrile and toluene as porogen. The experiments carried out by molecularly imprinted solid phase extraction (MISPE) in cartridges demonstrated the imprint effect in both imprinted polymers. MIP–DVB enabled a much higher breakthrough volume than MIP–EDMA, and thus was selected for further experiments. The ability of this MIP for the selective recognition of other benzimidazole compounds (albendazole, benomyl, carbendazim, fenbendazole, flubendazole and fuberidazole) was evaluated. The obtained results revealed the high selectivity of the imprinted polymer towards all the selected benzimidazole compounds.An off-line analytical methodology based on a MISPE procedure has been developed for the determination of benzimidazole compounds in tap, river and well water samples at concentration levels below the legislated maximum concentration levels (MCLs) with quantitative recoveries. Additionally, an on-line preconcentration procedure based on the use of a molecularly imprinted polymer as selective stationary phase in HPLC is proposed as a fast screening method for the evaluation of the presence of benzimidazole compounds in water samples.     

核-壳型赤藓红分子印迹聚合物的制备及吸附性能的评价

以氨基化修饰的SiO_2为内核,人工合成色素赤藓红为模板,甲醇/水为溶剂,4-乙烯基吡啶为功能单体,二甲基丙烯酸乙二醇酯为交联剂,偶氮二异丁腈为引发剂,采用表面印迹技术,制备核-壳型赤藓红分子印迹聚合物。通过红外光谱对其结构进行表征,并通过动力学吸附、等温饱和吸附和实际样品加标实验对其吸附性能进行评价。结果表明,核-壳型赤藓红分子印迹聚合物具有较快的吸附能力,在15min左右达到吸附平衡,有较好的吸附容量,能够从复杂的食品样品中选择性吸附模板,且回收可达85%。