【作者】 吴文镶；

【导师】 杨更亮；

【作者基本信息】 河北大学 ， 分析化学， 2005， 硕士

【摘要】 分子印迹技术是指一种可以合成对指定分子具有专一性识别位点的聚合物的技术。近年来,分子印迹技术因其卓越的分子识别性能,在色谱分离,固相萃取,人工受体,酶模拟催化剂,以及传感器等研究领域引起了广泛的关注。本文应用分子印迹技术,分别以三唑醇、腈菌唑为印迹分子,采用本体聚合法、原位聚合法制备了不规则型、连续整体型具有特定识别和分离性能的分子印迹聚合物,用平衡吸附实验研究了其吸附性能。并用作高效液相色谱固定相实现了腈菌唑与类似物的分离,同时考察了分子识别过程中的影响因素。本文分为如下三个部分: 第一章:介绍了分子印迹技术的原理、研究应用和进展状况。 第二章:采用本体聚合的方法合成了对农药三唑醇有特异性作用的分子印迹聚合物。通过平衡吸附实验,评价了其对三唑醇的亲和力和选择性。与非印迹聚合物相比,分子印迹聚合物对三唑醇表现了较强的亲和力;以甲基丙烯酸为功能单体,三唑醇为模板的分子印迹聚合物,通过Scatchard分析,结果显示,该印迹聚合物上存在两种吸附位点。用多点结合模型计算两类不同结合位点的离解常数为K_d1=2.80×10^-4 mol/L,,K_d2=9.71×10^-3 mol/L。底物选择性实验表明,与其它结构相似的分子相比,该聚合物对三唑醇显示很强的结合能力。 第三章:采用原位聚合法,以腈菌唑为印迹分子,制备了具有特定识别性能的棒状分子印迹聚合物。将所得的聚合物用作高效液相色谱的固定相,研究了对结构类似物拆分能力。结果表明,在以甲醇:水=6:4的条件下两种结构类似物可以得到基线分离。同时考察流动相中醋酸含量对分离的影响,论证了分子印迹聚合物选择性专一的作用机理,其作用机理是多种作用的综合结果,除了形状识别以外,氢键作用在分子识别中起到至关重要的作用。更多还原

【Abstract】 Molecular imprinting is a technique to prepare polymers with recognition sites having a predetermined selectivity for given molecules. Much more attention has been paid to this technique in recent years. Molecularly imprinted polymers (MIPs) have been applied to chrornatographic stationary phase, artificial antibodies, catalysts, sensors and drug assay tools. In this thesis, A molecular template synthetic polymer highly selective for triadimenol (myclobutanil) was prepared by molecular imprinting technique (MIT) and have been used as HPLC stationary phases. The binding capacity was studied by equilibrium binding test Effects of mobile phase composition on retention and separation factor were investigated. There are three chapters in this thesis.In Chapter I, the principle of MIT, polymerization methods, application of this technique and its future developments were introduced.In Chapter II, A molecular imprinting polymer particular effect for triadimenol was prepared by molecular imprinting technique. Its binding and selectivity to triadimenol were evaluated by batch adsorption experiments. Triadimenol-imprinted polymer exhibited higher affinity to triadimenol compared to non-imprinted polymer, Scatchard analysis indicated that the imprinted polymer using methacrylic acid (MAA) as functional monomer could form two kinds of binding sites by noncovalent interactions . The multiple-sites binding model was used to calculate the maximum number of binding sites and dissociation constants. The dissociation constants were estimated to be 2.80×10~-4mol/L and 9.71×10~-3 mol/L .The selective binding experiment for substrates indicated that the polymer gave much higher affinity and selectivity for triadimenol than analogues.In Chapter III, myclobutanil has been employed as templates for the preparation of in-situ molecularly imprinted polymer rods for use as liquid chromatographic stationary phases. The preparation procedure was simple and easy. The recognition of the molecularly imprinted polymer rod was evaluated by comparing the retention values of myclobutanil and its analogues. The mixture of the two close analogues, myclobutanil and paclobutrazol can be baseline separated when the mobile solution is composed of methanol:water=4:6. Effects of acetic acid mobile phase composition on retention were investigated. Molecular recognition mechanism of myclobutanil-imprintedpolymer was proposed. The results indicated that hydrogenolysis effect dominated retention mechanism in no polarity media as well as shape recognition.更多还原