钙和钒离子对钒-溴过氧化物酶催化H_2O_2氧化环己烯反应的影响  

Effects of Calcium and Vanadium Ions on the Epoxidation of Cyclohexene with H_2O_2 Catalyzed by Vanadium Bromoperoxidase

作　　者：章表明[1,2] 曹旭鹏[1] 薛松[1] 肖通虎[3] 张卫[1,4] 

机构地区：[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

出　　处：《催化学报》2010年第10期1293-1299,共7页

基　　金：国家重点基础研究发展计划(973计划;2009CB724700);中国科学院知识创新工程重要方向项目(KSCX2-YW-G-073);浙江省自然科学基金(Y407353)

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1.0mmol/L钒离子和1.0mmol/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4.79g/(h·L),对H2O2的收率为74%,均比文献最高值提高了78%.Vanadium bromoperoxidase （V-BPO） from a marine macro-alga Corallina officinalis can catalyze the epoxidation of cyclohex-ene 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 productivity. 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.

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 

分 类 号：O643.32[理学—物理化学]