新型钒卤代过氧化物酶模型化合物的合成、结构及仿生催化活性

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (5): 1025.

新型钒卤代过氧化物酶模型化合物的合成、结构及仿生催化活性

曹运珠¹,李章朋¹,邢永恒¹,魏东明¹,蒲志凤²,葛茂发²,施展³

1. 辽宁师范大学化学化工学院, 大连 116029;
2. 中国科学院北京化学研究所, 北京 100080;
3. 吉林大学化学学院, 无机合成与制备化学国家重点实验室, 长春 130012

收稿日期:2010-09-09 修回日期:2010-11-18 出版日期:2011-05-10 发布日期:2011-04-11
通讯作者: 邢永恒 E-mail:xingyongheng2000@163.com
基金资助:
国家自然科学基金(批准号: 21071071)、吉林大学无机合成与制备化学国家重点实验室开放课题基金(批准号: 2010-15)和大连市教育基金(批准号: 2009J21DW004)资助.

Synthesis, Structure and Mimic Catalytic Activity of Novel Vanadium Haloperoxidase Model Complexes

CAO Yun-Zhu¹, LI Zhang-Peng¹, XING Yong-Heng^1*, WEI Dong-Ming¹, PU Zhi-Feng², GE Mao-Fa², SHI Zhan³

1. College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China;
2. Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China;
3. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China

Received:2010-09-09 Revised:2010-11-18 Online:2011-05-10 Published:2011-04-11
Contact: XING Yong-Heng E-mail:xingyongheng2000@163.com
Supported by:
国家自然科学基金(批准号: 21071071)、吉林大学无机合成与制备化学国家重点实验室开放课题基金(批准号: 2010-15)和大连市教育基金(批准号: 2009J21DW004)资助.

摘要/Abstract

摘要： 为模拟卤代过氧化物酶活性中心钒的配位环境, 我们设计合成了系列聚吡唑硼酸盐钒氧化合物, VO(HB(3,5-Me2pz)3)(3,5-Me2pz)(HOOCCH2CH2COO)和VO(HB(3,5-Me2pz)3)(3,5-Me2pz)(C5H4NCOO), 通过X-ray单晶衍射方法确定了它们的结构. 基于钒(V)在水体系中弱酸性条件下具有催化苯酚红溴化成溴酚蓝的特性, 我们对蝎型钒(IV)氧化合物进行了大量的实验, 结果发现类似的条件下蝎型钒(IV)氧化合物同样存在仿生催化活性, 并运用分子轨道理论对催化原理加以分析.

关键词: 卤代过氧化酶, 仿生催化活性, 聚吡唑硼酸盐, 钒(IV)氧化合物, 晶体结构

Abstract: In order to mimicking the active center of the VHPO, we designed and synthesized a series of oxovanadium complexes containing poly(pyrazolyl)borate ligands: VO(HB(3,5-Me2pz)3)(3,5-Me2pz)(HOOCCH2CH2COO) and VO(HB(3,5-Me2pz)3)(3,5-Me2pz)(C5H4N-COO), and they have been characterized by X-ray single crystal diffraction. Based on vanadium(V) complexes catalyzing the visible conversion of phenol red to bromophenol blue under weak-acid conditions, we investigated the role of the oxovanadium complexes in the bromide oxidation reaction. It is found that the oxovanadium (IV) complexes can be considered as potential functional model of vanadium-dependent haloperoxidases. And the mechanism of the catalytic reaction is analyzed by molecular orbital theory.

Key words: Haloperoxidases, Mimic catalytic activity, Poly(pyrazolyl)borate, Oxovanadium (IV) complex, Crystal structure

中图分类号:

0614

TrendMD:

曹运珠李章朋邢永恒魏东明蒲志凤葛茂发施展. 新型钒卤代过氧化物酶模型化合物的合成、结构及仿生催化活性. 高等学校化学学报, 2011, 32(5): 1025.

CAO Yun-Zhu, LI Zhang-Peng, XING Yong-Heng*, WEI Dong-Ming, PU Zhi-Feng, GE Mao-Fa, SHI Zhan. Synthesis, Structure and Mimic Catalytic Activity of Novel Vanadium Haloperoxidase Model Complexes. Chem. J. Chinese Universities, 2011, 32(5): 1025.

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