摘要
分子印迹技术是近年来出现的一种对目标分子具有预定选择性识别的新技术。分子印迹聚合物中由于含有和目标分子高度互补的空穴结构,因而其往往表现出惊人的专一识别性。此外,它还具有物理性质及化学性质稳定、制备简单、成本低等优点,现已在色谱分离、传感器、模拟酶催化、膜分离及固相萃取等许多领域得到越来越广泛的应用。利用原位聚合制备的分子印迹整体柱不但具有分子印迹聚合物的高选择性,还具有整体柱制备过程简单、重复性好、柱压低以及模板分子用量少等优点。利用本体聚合制备的分子印迹聚合物对印迹分子具有良好的选择性和识别特性,且该方法具有制备装置简单,条件易于控制,便于普及等优点。基于上述两种方法各自的优点,本论文制备了几种印迹聚合物,并研究了其对环境中残留农药、药物分子及植物激素的识别选择性能。由于生物识别一般在水中进行,因此研究了水相中分子印迹聚合物的应用。这些研究成果不仅拓展了分子印迹在分析化学中的应用,而且对于生物样品的分离和纯化,具有重要意义。研究的主要内容有:
(1)以2,4-二氯苯氧乙酸分子为模板,采用热引发原位聚合法合成了高效液相色谱固定相的整体柱。用红外光谱、扫描电镜、比表面积分析对聚合物进行了表征。考察了模板分子在不同条件下合成的印迹整体柱及空白整体柱上容量因子的变化规律,同时探讨了流动相中甲醇的含量、pH值、流速对印迹整体柱分离性能的影响。结果表明:在优化的合成条件下制备的分子印迹整体柱能够将2,4-二氯苯氧乙酸及其结构类似物苯氧乙酸完全分离开。并用其进行了柑桔提取液分离测试,结果满意。
(2)以柚皮素分子为模板,采用热引发原位聚合法制备了柚皮素分子印迹整体柱,并将其作为高效液相色谱固定相,通过高效液相色谱对其识别性能进行研究。优化了聚合反应条件,即考察了模板分子在不同聚合条件下合成的印迹整体柱及空白整体柱上容量因子的变化规律,同时探讨了流动相中水的含量、pH值对印迹整体柱分离性能的影响。用扫描电镜、比表面积分析对聚合物进行了表征。对传统中药中的柚皮素成分进行了检测,结果令人满意。
(3)以对氯苯氧乙酸为模板分子,采用热引发本体聚合法合成了分子印迹聚合物。为了研究聚合物的结合性质,分别测定了印迹聚合物与空白聚合物的结合等温线。与空白聚合物相比,印迹聚合物对模板分子表现出了更高的结合能力。Scatchard分析表明在所研究的浓度范围内,分子印迹聚合物中只存在一种等价结合位点。同时研究了印迹聚合物对模板分子及其结构类似物的选择性,证实了印迹聚合物对模板分子表现出更高选择识别能力。
Molecular Imprinting Technique is a new technique, which have the predetermined selectivity and recognition ability for the target molecules. Molecular imprinted polymers (MIPs) have cavity structure which is highly complementary to target molecule, as a result, the specificity recognition capability is very surprising.In addition, the stability of physical and chemical property, simple preparation, and low cost of molecularly imprinted polymers have led to their applications in many fields such as chromatographic separation, sensors, mimic enzyme catalysis, membrane separation and solid phase extraction. The molecularly imprinted monolithic columns (MIMC) prepared by in situ polymerization of monomers have not only the high stereo selectivity of MIPs, but also some advantages of simple preparation procedures, good reproducibility, low backpressure of column and low-consumption of template molecules. MIPs prepared by bulk polymerization have not only high selectivity and good recognition ability, but also some advantages of simple preparation device, easily controlled condition, conveniently popularization. In this paper, several MIPs based on the above-mentioned methods have been developed, and successfully applied to selectivity and recognition ability of environmental pesticide residue, some drugs, phytohormone. However, for some biological samples whose biological recognition mainly occurs in aqueous solution and the application of MIPs were limited to some extent. So it is extremely important to prepare MIPs that are able to go on biological recognition in aqueous solutions. These results extended the applications of MIPs in analytical chemistry. The foucus of this paper has been listed as follow:
(1) Monolithic columns(MTC) were synthesized using 2,4-dichlorophenoxyacetic acid(2,4-D) as template molecules by in situ thermal-initiated polymerization method, which was used to be the stationary phase of the high performance liquid chromatography. The polymers were characterized with infrared spectrum, morphology was also analyzed with scanning electron microscopy and surface area analysis. The trends of retention factors of imprinted and blank MTC synthesized under different conditions were investigated. Furthermore, effects of methanol content, pH and flow rate on the separation performance of MIMC were discussed. Result show: The stationary phase of MIMC synthesized under optimization of preparation conditions could entirely separate 2,4-D and its analogues phenoxyacetic acid. The separation of 2,4-D from the distill liquid of orange on MIMC were tested with good result.
(2) Monolithic columns were synthesized using naringenin as template molecules by in situ thermal-initiated polymerization method, which was used to be the stationary phase of the high performance liquid chromatography, selectivity and recognition ability of MIPs were studied. The trends of retention factors of imprinted and blank MTC synthesized under different conditions were investigated.Furthermore, effects of methanol content, pH on the separation performance of MIMC were discussed. The polymers morphology were characterized with scanning electron microscopy and surface area analysis. The MIPs has been successfully applied to the determination of naringenin in the Chinese traditional medicine with good results.
(3) Molecular imprinted polymers were prepared using 4-chlorophenoxyacetic acid(4-CPA) as template molecules by thermal-initiated bulk polymerization method. In order to investigate the binding performance of the MIPs and blank polymers, their binding isotherm was determined. The polymer show much higher binding capacity for 4-CPA than the non-imprinted polymer with the same chemical composition. Scatchard analysis showed only one class of binding sites was formed in the imprinted polymer under the studied concentration. The experiment which MIPs was studied the selective recognition to 4-CPA and analogs, revealed that MIPs showed higher and better selective recognition abilities to 4-CPA.
引文
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