【作者】 赵川德；

【导师】 张海霞；

【作者基本信息】 兰州大学 ， 分析化学， 2011， 博士

【摘要】 分子印迹技术从仿生角度采用人工模拟方法制备对模板分子具有特异性识别作用的聚合物,在化学仿生传感器,催化,色谱分离,固相萃取,天然抗体模拟及模拟酶催化中显示出广泛的应用前景。随着生命科学、材料科学和环境科学等学科的迅速发展,人们对自身健康和环境的要求提高,给分析科学带来了新的挑战和机遇。随着分析样品的多样化和复杂化,对样品中干扰物的去除及痕量组分的富集和检测成为最突出的问题。要实现样品的富集分离通常需要借助选择吸附容量大、选择性高的吸附材料和合适的分离手段。本论文合成了几种分子印迹材料并与高效液相色谱联用检测食品中的污染物。主要进行了以下几方面的研究工作。1.以环境雌激素污染物己烯雌酚(DES)为模板分子,凹凸棒(ATP)为基质,丙烯酰胺为功能单体,N,N’-亚甲基双丙烯酰胺为交联剂合成分子印迹材料,使用红外光谱(FTIR),透射电镜(TEM)和静态吸附实验进行了材料表征。发现以ATP为基质的分子印迹具有更高的吸附量和更快的传质动力学。将制备的DES印迹材料应用到固相萃取技术中,研究了分子印迹固相萃取柱的选择性、稳定性和可靠性,并与高效液相色谱仪联用,分析检测鱼肉样品中的己烯雌酚并建立了相应的分析方法。2.以苏丹红染料中苏丹Ⅰ(SudanⅠ)为模板分子,ATP为基质,2-乙烯基吡啶为功能单体,乙二醇二甲基丙烯酸酯为交联剂合成分子印迹材料,使用FTIR, TEM和静态吸附实验进行了材料表征。对上一工作中通过超支化反应对凹凸棒表面进行双键修饰的方法进行了改进,采用3-甲基丙烯酸丙酯基三甲氧基硅烷进行修饰,简化了以ATP为基质的分子印迹的合成方法,有利于ATP作为分子印迹基质的广泛应用。SudanⅠ分子印迹在静态和动态选择性实验中对SudanⅠ-Ⅳ显示了良好的选择性,并将它与高效液相色谱联用在线固相萃取和检测了水样、番茄酱和火腿肠中的SudanⅠ-Ⅳ.3.以β-萘酚为模板分子,ATP为基质,甲基丙烯酸酯基-β-环糊精为功能单体(CyD),N,N’-亚甲基双丙烯酰胺为交联剂合成分子印迹材料。通过不同的超声功率制备了印迹材料并与传统热聚合制备的印迹材料进行的选择性比较实验,发现超声制备的印迹材料比热聚合得到的印迹材料有更好的选择性和更快的传质动力学。选择了15 KHz超声功率下制备的印迹材料与高效液相色谱联用在线固相萃取和检测牛奶中的雌二醇,雌三醇,雌酮和己烯雌酚并建立的相应的分析方法,该方法展示了良好的重现性和回收率。4.将未衍生化的β-环糊精(p-CD)和甲基丙烯酸为功能单体,反式白藜芦醇(RES)为模板分子,乙二醇二甲基丙烯酸酯为交联剂制备了印迹聚合物。该工作中,β-CD通过自组装的方式串在甲基丙烯酸和乙二醇二甲基丙烯酸酯的聚合物链上与模板分子发生相互作用,避免了相关文献中对双键衍生后β-CD的分离和纯化的繁琐工作。我们将制备的RES印迹材料填装到固相萃取柱中离线固相萃取了酒样中的RES,并用高效液相色谱检测。通过比较印迹材料和空白材料在实际样品中对RES的选择性,发现印迹材料在实际样品中体现了良好的选择性。更多还原

【Abstract】 Molecular Imprinting Technique is originated from bionic to prepare polymers with recognition specificity to template molecules by manual method. Molecular Imprinting Polymers (MIPs) have exhibited extensive application prospect in sensors, catalysis, SPE, chromatography separation and as artificial antibodies in binding assays.With the rapid development of life sciences, materials science and environmental science, and the growing concerns over human health and the environment, analytical science is facing the new opportunity and rigorous challenge. Owing to the diverse and complex of samples, pre-concentration and analysis of trace elements is still necessary before the more aceurate measurement by analytical instruments, which depend on different adsorption materials with higher selectivity and larger adsorption capacity and appropriate separation methods. In this thesis, several new MIPs are synthesized and coupled with high performance liquid chromatography(HPLC) to determine the additive agents in food sample. The more detailed novelty of this research can be categorized as following:1. Using nanoattapulgite as matrix, acrylamide as functional monomer and N, N’-methylene bisacrylamide as crosslinker, both diethylstilbestrol (DES) surface imprinted polymer and non-imprinted polymer were synthesized. The DES imprinted sorbent and non-imprinted sorbent were characterized by FTTR and static adsorption capacity. Compared with each other, the DES imprinted polymer is superior to non-imprinted polymer in adsorption capacity, selectivity and mass transfer property. As the packing material of solid-phase extraction, the DES imprinted polymer has been applied to concentrating DES in pond water and fish samples. A corresponding analytical method to determine diethylstilbestrol has been developed.2. A novel molecularly imprinted polymer was synthesized with attapulgite employed as matrix, sudan I as template molecule,2-vinylpyridine as functional monomer and ethylene glycol dimethacrylate as cross-linking agent, respectively. The imprinted polymer was characterized by the FTIR and TEM. We developed a more simple approach to synthesize sudan I MIP. The vinyl functional group was easily modified onto the surface of ATP with MATMS by silane coupling reaction, and then the modified ATP was directly used as the matrix of MIP, which was time-saving, economic and beneficial to the development of ATP matrix based MIP. Additionally, the MIP-SPE column based on sudan I MIP was prepared and used for the simultaneous on-line SPE to determine sudan I-IV in Yellow River water, tomato sauce and sausage samples.3. Using nanoattapulgite as matrix,β-naphthol as template, methacryloyl-β-cyclodextrins (CyD) as functional monomer and N, N’-methylene bisacrylamide as crosslinker, a novel molecularly imprinted polymer was synthesized by different ultrasonic frequencies and traditional sources of heat. The two kinds of imprinted polymer were characterized by FTTR, TEM and static adsorption capacity. Compared with each other, the DES imprinted polymer prepared by ultrasonic superior to by traditional heat sources in selectivity and mass transfer property to estrone, estradiol, estriol and DES. We chose the MIP prepared at 15 KHz ultrasonic frequencies (SMIP) to simultaneously on-line extract four estrogens in samples from milk. The proposed methods showed the SMIP was feasible in the determination of these estrogens in real samples.4. An imprinted polymer was synthesized using methacrylic acid (MAA) and P-cyclodextrins (CD) as bi-functional monomer for solid-phase extraction of trans-resveratrol (RES).β-CD could self-assembly in the imprinted polymer, which showed that CD could improve the sorbent capacity and the selectivity for RES. Meanwhile, it could avoid to the derivative reaction of CD. The bi-functional monomer imprinted polymers were used as the sorbent for solid-phase extraction to determine RES in wine and Chinese liquor samples. The molecular imprinted polymer solid-phase extraction-high performance liquid chromatography (MIP-SPE-HPLC) method showed higher selectivity and good recoveries higher than 87.9%.更多还原