【作者】 张立永；

【导师】 成国祥；

【作者基本信息】 天津大学 ， 材料学， 2003， 博士

【摘要】 分子印迹技术是一种制备对特定分子具有专一识别性能的聚合物（MIP）的技术，MIP对模板分子的识别具有预定性、专一性和实用性等优点而在分离提纯、免疫测定、生物模拟以及痕量分析等领域显示出广阔的应用前景。本文对分子印迹技术的基本原理、分子印迹聚合物的制备和应用进行了较为全面的综述，对分子印迹技术当前存在的问题和未来的发展趋势进行了分析和展望。分别采用种子溶胀悬浮聚合法、悬浮聚合法和乳液聚合法，在水相中体系制备得到了一系列氨基酸和药物印迹的分子印迹聚合物微球（MIPM）；采用扫描电镜、热失重分析、电子能谱分析、固相（微）萃取等技术对制备所得的MIPM进行了分析和表征；采用双模板印迹的方法对水相中MIPM的印迹和识别机理进行了探讨。研究表明，种子溶胀悬浮聚合法和悬浮聚合法均能在水性体系中制备得到50-300?m的、具有大孔结构的MIPM，前者的产物具有相对较窄的粒径分布，但后者的制备工艺则较简单、制备周期也较短；溶胀剂、搅拌速度、种球用量、分散剂、稀释剂和致孔剂是影响产物微球形态的主要因素；乳液聚合法能够制备得到0.16-0.56?m之间的分子印迹聚合物微球（MIPM），乳化剂、加料方式以及聚合体系的pH值是影响产物微球形态的主要因素。研究还表明,所得的印迹物对模板的吸附满足Langmiur吸附模型，其吸附性能受到粒子形态、聚合物组成等因素的影响；印迹物对模板分子都表现出专一识别特性和良好的再生使用性能，对药物混合物的拆分和痕量组分的富集的效果也很显著；印迹物的分子识别性能主要受到功能单体的种类和用量、聚合物母体的交联度、识别环境的pH值等因素的影响；水相中模板和功能单体主要以静电作用和疏水作用相结合，酸性模板宜选用碱性功能单体，且适宜的环境pH在3.6-5.7；碱性模板宜选用酸性功能单体，且适宜的环境pH在8.0-10.5；采用抗原表位的印迹方法可以小分子为模板制备得到对生物大分子具有专一识别特性的MIPM，这种方法为结构明确或抗原表位部分结构明确的大分子的印迹提供了新的途径。更多还原

【Abstract】 Molecular imprinting technique (MIT) is becoming increasingly recognized as a powerful technique of preparing synthetic polymers that contain tailor-made recognition sides for certain molecules. It has an extensive application in purification, separation, immunoassay, enrichment, biomimics and other relevant fields for its predetermination, specificity and practicability of molecule recognition.This thesis gives a brief overview of the development of the principle of MIT, the preparation and application of molecularly imprinted polymers (MIP), and offers an insight into the problems met with and how the area is likely to evolve in the near future. Some amino acids and drugs imprinted spheres (MIPM ) were prepared via seeds swelling and suspension polymerization, suspension polymerization and emulsion polymerization. The physical and chemical properties of the polymers were analyzed by scanning electron microscope, thermogravimetric analyzer, electron spectrum and solid phase extraction (microextraction) technology. The imprinting and recognizing principle of MIPM in water was studied through bi-templates imprinting method as well.It was showed that MIPM between 50-300?m with macro-pores could be prepared via both seeds swelling and suspension polymerization method and suspension polymerization method, the former method could prepared the MIPM with narrower size distribution while the later one was easier to carry out and more time-saving. The morphology of the MIPM was influenced by many factors including swelling solvent, stirring speed, dosage of seeds, dispersant, dilute and progenic solvent. MIPM between 0.16-0.56?m was prepared via emulsion polymerization method, the morphology of the MIPM was mainly influenced by emulsifier, mode of monomers-addition and pH value of the polymerizing system.The result also showed that MIPM prepared in this thesis adsorbed their templates in the way of Langmiur, and their adsorption properties were influenced <WP=5>by the morphology of the beads and the composition of the polymers. The imprinted beads all exhibited a specific recognition to their templates, a nice regeneration property, a good separating ability to compound and remarkable enriching ability to tiny substance, and these abilities of imprinted beads were influenced by the functional monomers, the cross-linking degree of polymeric matrix and the pH value of the recognizing system etc. Functional monomers (FM) were showed to combine the templates mainly through electrostatic and hydrophobic interactions in the water system, basic FM was more suitable to acidic templates and exhibited higher recognizing ability in the system with the pH of 3.6-5.7, while acidic FM was more suitable to basic templates and exhibited higher recognizing ability in the system with the pH of 8.0-10.5. MIPM with the specific recognizing ability to biomacromolecules were prepared though epitope approach using small molecules as templates, and this approach offers a novel and feasible method of the imprinting of macromolecules on the condition that the molecule structure of the macromolecule or the epitope part is specific.更多还原