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脂肪酶催化拆分外消旋2-甲基-1-丁醇的研究
Study on Resolution of Racemic 2-methyl-1-butanol Catalyzed by Lipase
【作者】 江丽葵;
【导师】 宋航;
【作者基本信息】 四川大学 , 化学工程, 2002, 硕士
【摘要】 酶具有高效率和高度立体选择性,是一般催化剂所无法比拟的,它们在有机合成中有极其重要的应用价值。近年来,随着非水相酶催化理论的发展,非水介质中酶催化反应正获得越来越多的研究和应用,尤其是脂肪酶在非水有机溶剂中催化拆分制备手性物质。 本文应用非水有机溶剂中脂肪酶催化酯交换反应的理论,用猪胰脂肪酶(PPL)和酵母脂肪酶(CCL)催化外消旋2-甲基-1-丁醇与三丁酸甘油酯的酯交换反应,以获得高纯度的(S)-2-甲基-1-丁醇。为了提高酶催化的活性和稳定性,利用吸附法将两种酶固定在几种疏水性程度不同的载体上,考察了不同的固定化方式、不同性质的载体、固定化温度、固定化时间等因素对固定化效果的影响,寻求这两种酶的较优的固定化条件。利用游离脂肪酶及其固定化酶在非水相中催化拆分外消旋2-甲基-1-丁醇,考察了有机溶剂、固定化酶量、反应时间、底物配比、水含量等因素对酯交换反应的影响。 实验结果表明,在实验确定的反应条件下:有机相中通过PPL,CCL游离酶及其固定化酶催化酯交换反应拆分外消旋2-甲基-1-丁醇,四种酶都有很好的催化活性和立体选择性;固定化酶的热稳定性及操作稳定性优于游离酶。用减压精馏方法分离反应生成的混合物,得到高纯度的光学活性2-甲基-1-丁醇。实验中用高效液相色谱检测酯交换的反应进度,气相色谱仪检测减压精馏提纯的2-甲基-1-丁醇的纯度,旋光仪测定最终产物(S)-2-甲基-1-丁醇的旋光度。产品(S)2-甲基-1-丁醇的光学纯度达到98%以上。
【Abstract】 Lipase have great potential as catalysts for use in organic synthesis, because of their high catalytic efficiency and stereoselectivity. As techniques for lowering lipase cost available, lipase catalyzed organic reactions are of great value as a new synthesis method. Enzymatic catalysis in organic solvent is one of the most interesting topics. Because of the importance of chiral drugs, considerable efforts have been made in developing bio-transformation for the production of chiral drugs.Some important alcohols are synthesized through transesterification processes using an ester and an alcohol. In this paper, efficient resolution of a racemic 2-methyl-1-butanol was achieved by Candida cylindracea Lipase (CCL) and Porcine Pancreatic Lipase (PPL) catalysed transesterification in non-aqueous organic media. To overcome the problems in using free lipases, immobilized lipases have been used as catalysts on supports. To find the optimum factors such as PH , temperature ,the amount of lipase, the different supports and different immobilized methods, CCL and PPL were immobilized on kinds of supports by different methods . The dispersion of lipase in organic solvent was improved effectively by means of adsorbing lipase on GDX-102. It was found that the immobilized lipase in organic media remained a very high activity.The free and immobilized lipase were catalyzed the transesterification of 2-methyl-l-butanol and triburyrin. The influences of organic solvent , water content , ratio of substrates , immobilized lipase content , reaction time and temperature on resolution were systematic studied. In experimentconditions, thermal stability and operation stability of the immobilized lipase were more excellent than those of the free lipase. Experimental observations indicated that the lipase can be reused. The optical purities of productds can over 98%.
【Key words】 lipase; lipase transesterification; (s)-2-methyl-1-butanol; immobilized lipase;
- 【网络出版投稿人】 四川大学 【网络出版年期】2002年 02期
- 【分类号】O643.3
- 【下载频次】381