应用化学

• 研究论文 • 上一篇    下一篇

过氧钒配合物的合成、结构及模拟过氧化酶催化溴化动力学

陈晨2,张瑞2,王璇2,曹运珠2,白凤英1*,张小溪2,李光华3,施展3,邢永恒2   

  1. (辽宁师范大学1.生命科学学院;2.化学化工学院 大连116029;
    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:2012-11-23 修回日期:2013-04-11 出版日期:2013-12-10 发布日期:2013-12-10
  • 通讯作者: 白凤英,副教授; Tel:0411-82156987; Fax:0411-82159362; E-mail:baifengying2000@163.com; 研究方向:生物无机
  • 基金资助:
    国家自然科学基金资助项目(21071071),无机合成与制备化学国家重点实验室(吉林大学)开放课题基金(2013-05)

Synthesis, Structure and Mimic Haloperoxidase Catalytic Activity of Peroxovanadium Complexes

CHEN Chen2, ZHANG Rui2, WANG Xuan2, CAO Yunzhu2, BAI Fengying1*, ZHANG Xiaoxi2, LI Guanghua3, SHI Zhan3, XING Yongheng2   

  1. (1.College of Life Science,Liaoning Normal University;
    2.College of Chemistry and Chemical Engineering,Dalian 116029,China;
    3.State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,College of Chemistry,Jilin University,Changchun 130012,China)
  • Received:2012-11-23 Revised:2013-04-11 Online:2013-12-10 Published:2013-12-10
  • Contact: Feng Ying Bai

摘要: 根据模拟钒卤代过氧化物酶(V-HPOs)活性中心的配位环境,设计并合成了2种新型过氧钒配合物:Na[VO(O2)2(C10H8N2)]·8H2O(1)和K3H[(VO)2(O2)4(μ2-O)]·H2O(2),通过元素分析、红外光谱和紫外光谱对其进行了表征,并通过X射线单晶衍射方法确定了其结构。 配合物1晶体属于三斜晶系,空间群:P-1,a=0.7213(2) nm,b=1.1269(4) nm,c=1.3728(4) nm,α=68.349(4)°,β=89.178(4)°,γ=88.050(4)°,V=1.0365(6) nm3。 配合物2的晶体属于单斜晶系,空间群:P21/c,a=0.67047(12) nm,b=0.99503(18) nm,c=1.5817(3) nm,α=γ=90°,β=93.739(2)°,V=1.0530(3) nm3。 配合物1和2分别是五角双锥和八面体配位构型。 通过催化溴化反应活性研究发现,2种配合物均可作为潜在的钒卤代过氧化物酶模拟物。

关键词: 钒卤代过氧化物酶, 钒过氧配合物, 晶体结构, 催化活性

Abstract: Based on mimicking the environment of the active center of vanadium haloperoxidase(V-HPOs), we designed and synthesized two kinds of peroxovanadium complexes:Na[VO(O2)2(C10H8N2)]·8H2O(1) and K3H[(VO)2(O2)4(μ2-O)]·H2O(2), which were structurally characterized by X-ray single crystal diffraction, elemental analysis, IR and UV-Vis spectroscopies. Structural analyses reveal that complex 1 crystallized in an triclinic system with space group P-1, a=0.7213(2) nm, b=1.1269(4) nm, c=1.3728(4) nm, α=68.349(4)°, β=89.178(4) °, γ=88.050(4)°, V=1.0365(6) nm3 and the complex 2 crystallized in an monoclinic system with space group P21/c, a=0.67047(12) nm, b=0.99503(18) nm, c=1.5817(3) nm, α=γ=90°, β=93.739(2)°, V=1.0530(3) nm3. Complex 1 has a distorted pentagonal bipyramidal geometry, while complex 2 has a distorted octahedron geometry. In addition, by studying the bromination reaction activity, it shows that the peroxovanadium complexes can be considered as a potential functional model of bromoperoxidase.

Key words: vanadium haloperoxidase, peroxovanadium complex, crystal structure, catalytic activity

中图分类号: