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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (10): 1239-1246. 上一篇    下一篇

研究论文

咪唑/吡啶离子液体辅助氯过氧化物酶催化氧化环己烯的研究

张慧真1, 蒋育澄*,1,2, 胡满成1,2, 李淑妮1,2, 翟全国1,2   

  1. (1陕西师范大学化学与材料科学学院 西安 710062)
    (2陕西师范大学大分子科学陕西省重点实验室 西安 710062)
  • 投稿日期:2010-10-22 修回日期:2010-12-31 发布日期:2011-01-17
  • 通讯作者: 蒋育澄 E-mail:jyc@snnu.edu.cn
  • 基金资助:

    基于定位突变分子设计的氯过氧化物酶手性催化活性研究

Studies on the Oxidation of Cyclohexene Catalyzed by Chloroperoxidase in the Presence of Imidazole/pyridine Ionic Liquids

Zhang Huizhen1|Jiang Yucheng*,1,2|Hu Mancheng1,2|Li Shuni1,2|Zhai Quanguo1,2   

  1. (1 School of Chemistry and Materials Science, Shaanxi Normal University, Xi an 710062)
    (2 Key Laboratory of Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi an 710062)
  • Received:2010-10-22 Revised:2010-12-31 Published:2011-01-17
  • Contact: Yu-Cheng JIANG E-mail:jyc@snnu.edu.cn

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1214

被引次数

6

以氯过氧化物酶(CPO)催化、H2O2氧化实现环己烯的环境友好转化, 并通过溶剂工程调控和提高目标产物的产率. 研究结果表明缓冲液体系(PBS)中引入咪唑/吡啶类离子液体(ILs)时, 含量仅为1.5% (WILs/WPBS)时环己烯转化率即可提高31%. 酶促反应动力学参数Km的减小以及Kcat和Kcat/Km的增大表明引入离子液体时CPO对底物的亲和力及对底物识别的专一性得以改善, 导致转化数增大, 这是底物转化率有效提高的主要原因|此外, 紫外, 荧光及圆二色谱研究及产物组成分析表明离子液体在反应体系中具有多重功能: 相转移催化、诱导酶分子结构优化及调节产物组成. 由于反应基本在150 min内结束, 酶用量极少, 因此具有一定的产业化应用潜能.

关键词: 氯过氧化物酶, 环己烯, 咪唑/吡啶离子液体

The environmental friendly biotransformation of cyclohexene catalyzed by chloroperoxidase (CPO) with H2O2 as oxidant was carried out in this work. The yield of expected products was tuned and enhanced by solvent engineering. The results showed that the conversion of cyclohexene was enhanced 31% when only 1.5% (WILs/WPBS) of imidazole/pyridine ionic liquids (ILs) was introduced into the PBS buffer. The decrease of enzyme kinetic parameters Km and increase of Kcat and Kcat/Km indicated that both the affinity and specificity of CPO to the substrate were improved in the presence of ILs, resulting in the increase of turnover number. This was the main reason of conversion enhancement. Moreover, UV-vis, fluorescence and circular dichroism assay and analysis of products composition indicated that ILs played multiple functions in this enzyme-catalyzed reaction: phase transfer catalysis, inducing catalytically favorable conformation of CPO and tuning the composition of products. This enzymic-reaction was over within 150 min, and enzyme consumption was small. So, it has some potential utility in industry application.

Key words: chloroperoxidase, cyclohexene, imidazole/pyridine ionic liquids