【作者】 汪海萍；

【导师】 刘晓宁；

【作者基本信息】 南京工业大学 ， 生物工程， 2004， 硕士

【摘要】 聚合物作为试剂发展到现在,通过研究聚合物载体化反应进行有机合成已成为有机化学和功能高分子化学的一个重要的课题。聚苯乙烯作为聚合物载体的一种已为人们广泛的应用,论文选用自制的聚苯乙烯与二乙烯基苯共聚的、粒径单分散的微球作为聚合物载体,通过傅克酰基化反应在该聚苯乙烯微球上接上羧基基团制备聚合物试剂,并把该羧基化聚苯乙烯应用于固定化酶、正电子放射断层显像技术(PET)以及离子交换分离领域。在第一章中,本文概述了聚合物试剂的优点,制备方法,聚合物试剂的载体的性能、选用原则、分类和聚合物试剂的应用。在第二章中,本文用邻苯二甲酸酐作为酰基化试剂,运用傅克酰基化反应在粒径均一的聚苯乙烯微球上进行功能化得到羧基树脂,这种方法简单易行,制成的羧基树脂不同于其它由功能化单体聚合的羧基树脂,其羧基功能基团主要分布在微球的表面。在羧基树脂制备中,本文优化了反应的条件,即反应时间,反应温度等等,并着重讨论了混合溶剂中硝基苯对反应的影响。用所选优化条件,在担载量为0～2.88mmol/g范围内,可以由不同的邻苯二甲酸酐的量来控制获得预期担载量的羧基树脂。在第三章中,本文对第二章制备的羧基化聚苯乙烯进行了三方面的应用研究。1)测定了树脂的交换容量,pH滴定曲线,确定该树脂为典型的弱酸型阳离子交换树脂,且担载量越高的树脂其交换容量越高;2)研究了PET药物(脱氧胸腺嘧啶核苷,简称dT)的高分子化及优化了反应条件,在优化条件下羧基可完全被dT酯化,并可同时被环化;本文还通过氧化乙酰基聚苯乙烯制备了另一种羧基化聚苯乙烯,并研究了氧化反应的条件,根据氧化反应分步进行的原理,用分段的温度进行反应使氧化反应达到最优化。同时把这种氧化羧基树脂应用于PET药物(dT)的高分子化;3)基于“柔性固定化模型”的理论,用羧基化聚苯乙烯作为载体经与柔性链接枝后柔性固定化木瓜蛋白酶。研究结果发现,由本文制备的柔性载体进行酶的固定化,所得酶活力回收率是氨基手臂载体的2倍。更多还原

【Abstract】 Polymer as reagent has been developed to be an important task in the field of organic synthesis and functional polymer chemistry by studying polymer support reaction. Polystyrene as a support has been applied in a wide domain, in this paper, carboxylic group is connected on the polystyrene and DVB copolymer (PS), monodisperse microspheres, and this carboxylic PS can be used in ion exchange, enzyme immobilization and PET drug synthesis.In the first part, advantage, preparation method and application of polymer reagent, characteristic, principle, classification and application of polymer support are summarized.In the second part, a new functionalized polystyrene-based(PS)resin is synthesized using phthalic anhydride (PA) as acetylation reagent by Friedel-Crafts Acetylation. This preparation method is simple, and carboxylic group is mainly distributed on the surface of PS other than some carboxylic resins are prepared by functionalized monomer. This reaction conditions is optimized (including reaction time, temperature etc.) and effect of nitrobenzene is discussed deeply. The loading of carboxylic PS is controlled in the range of 0～2.88mmol/g according to amount of PA. In the last part, the product of the second part is used in the following three aspects. Firstly the carboxylic polystyrene is affirmed as a kind of weak acid cation exchange resin through mensurated ion-exchange capacity and pH metric titration curve, and high carboxylic loading resin has high ion-exchange capacity. Secondly it is used as a support of PET medicine(thymidine,dT) and optimizes this reaction conditions. In this optimum reaction conditions, the carboxyl could be completely esterified by dT and dT could be completely looped. Meanwhile, another carboxylic PS is prepared by oxidized acetylation PS, reaction condition is primarily studied and using incontinuous reaction temperature based on incontinuous reaction mechanism. This resin is also applied in PET drug (dT) support Finally, based on the “Flexible <WP=6>immobilized enzyme” model, using this resin as immobilization support, it is found that recovery of immobilized papain by PS-COO-DAS is twice equal to recovery of immobilized papain by PS-NH-GA.更多还原