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

Synthesis,Structure and Mimic Haloperoxidase Catalytic Activity of Peroxovanadium Complexes

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。

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 （ 02 ） 2 （ C10 Hs N2 ） ] ·8H2 O （ 1 ） and K3 H [ （ VO ） 2 （ 02 ） 4 （μ2-O） ] · n2 O （ 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, a=68.349（4）°, β =89. 178（4）°, T =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, a =β=90°, fl=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.