催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (10): 1293-1299.DOI: 10.3724/SP.J.1088.2010.00438

• 研究论文 • 上一篇    下一篇

钙和钒离子对钒-溴过氧化物酶催化 H2O2 氧化环己烯反应的影响

章表明 1,2, 曹旭鹏 1, 薛松 1, 肖通虎 3, 张卫 1,4   

  1. 1中国科学院大连化学物理研究所, 辽宁大连 116023; 2中国科学院研究生院, 北京 100049; 3宁波大学材料化学与工程学院, 浙江宁波 315211; 4弗林德斯大学海洋生物过程及生物产品研究中心, 阿德莱德 SA5042, 澳大利亚
  • 收稿日期:2010-10-25 出版日期:2010-10-25 发布日期:2014-03-04

Effects of Calcium and Vanadium Ions on the Epoxidation of Cyclohexene with H2O2 Catalyzed by Vanadium Bromoperoxidase

ZHANG Biaoming1,2, CAO Xupeng1, XUE Song1, XIAO Tonghu3, ZHANG Wei1,4,*   

  1. 1Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China; 2Graduate University of Chinese Academy of Sciences, Beijing 100049, China; 3Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang, China; 4Flinders Centre for Marine Bioprocessing and Bioproducts, Flinders University, Adelaide, SA5042, Australia
  • Received:2010-10-25 Online:2010-10-25 Published:2014-03-04

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摘要： 在溴化钾存在下, 大型海洋藻类珊瑚藻的钒-溴过氧化物酶 (V-BPO) 可在常温下催化 H2O2 环氧化环己烯生成环氧环己烷. 通过用含 1.0 mmol/L 钒离子和 1.0 mmol/L 钙离子的缓冲溶液透析 V-BPO, 用恒流泵向反应体系中连续添加 H2O2, 并优化其它反应条件, 可提高该催化反应时空收率. 在优化的反应条件下, 产物环氧环己烷的时空收率为 4.79 g/(h•L), 对 H2O2 的收率为 74%, 均比文献最高值提高了 78%.

关键词: 溴过氧化物酶, 钙离子, 钒离子, 环己烯, 过氧化氢, 环氧化反应, 环氧环己烷

Abstract: Vanadium bromoperoxidase (V-BPO) from a marine macro-alga Corallina officinalis can catalyze the epoxidation of cyclohexene in the presence of KBr to form epoxycyclohexane using H2O2 as the oxidant. A process intensification strategy has been developed by the integration of V-BPO pretreatment, continuous feeding of H2O2, and optimizing reaction conditions in order to improve the epoxidation pro-ductivity. The BPO activity and thermostability increased significantly when the V-BPO solution was dialyzed with a buffer containing 1.0 mmol/L vanadium ion and 1.0 mmol/L calcium ion. The apparent enzyme activity was improved when the H2O2 was fed continuously using a constant flow pump. When combined with the optimal reaction conditions (including buffer, pH, temperature, enzyme concentration, and KBr and H2O2 concentrations), the space-time yield of epoxycyclohexane and its yield to hydrogen peroxide reached 4.79 g/(L•h) and 74%, respectively. These values are 78% increasing than the highest values reported previously.

Key words: bromoperoxidase, calcium ion, vanadium ion, cyclohexene, hydrogen peroxide, epoxidation, epoxycyclohexane