过渡金属-联咪唑-Dawson型钨磷酸盐杂化化合物的酶固定化性能  

Properties of Transition Metal-biimidazole-Dawson-type Tungstophosphate Hybrid Compounds as Supports for Enzyme Immobilization

作　　者：朱浩天[1,2] 金美秀 唐文思 苏芳 李阳光[2] ZHU Haotian;JIN Meixiu;TANG Wensi;SU Fang;LI Yangguang(Key Laboratory of Polyoxometalate and Reticular Material Chemistry,Ministry of Education,Faculty of Chemistry,Northeast Normal University,Changchun 130024,China;School of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian 116029,China)

机构地区：[1]辽宁师范大学化学化工学院,大连116029 [2]多金属氧酸盐与网状材料化学教育部重点实验室,东北师范大学化学学院,长春130024

出　　处：《高等学校化学学报》2022年第11期42-52,共11页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22071020,22171041,21771033)资助。

摘　　要：利用水热法和直接沉淀法,设计合成了5例由过渡金属(TM)-联咪唑配阳离子与Dawson型钨磷酸阴离子构成的多金属氧酸盐(POM)基有机-无机杂化化合物[Ni(H_(2)biim)_(3)]_(4)[Ni(H_(2)biim)_(2)(P_(2)W_(18)O_(62))_(2)]·2H_(2)O(1),[Co^(Ⅲ)(H_(2)biim)_(3)]_(2)[P_(2)W_(18)O_(62)]·8H_(2)O(2),[Cu(H_(2)biim)_(2)]_(3)[P_(2)W_(18)O_(62)]·4H_(2)O(3),[Co^(Ⅱ)(H_(2)biim)_(3)]_(2)H_(2)[P_(2)W_(18)O_(62)]·9H_(2)O(4)和[Ni(H_(2)biim)_(3)]_(3)[P_(2)W_(18)O_(62)]·2H_(2)O(5);并利用X射线单晶衍射分析(SC-XRD)、红外光谱(IR)和热重-差热分析(TG-DTA)等对其进行了表征.化合物1~5作为载体用于固定辣根过氧化物酶(HRP)时,显示出了较高的酶固定化能力.另外,利用圆二色光谱(CD)和激光扫描共聚焦显微镜(LSCM)等方法评价了固定化酶HRP/1~HRP/5的重复使用性、储存稳定性和检测过氧化氢(H_(2)O_(2))的性能.由于该类POMs与HRP间存在强的相互作用,利用简单的物理吸附法即可实现POMs对HRP的固载.POMs对酶的固定不但提高了HRP对使用及储存环境的耐受性,同时也拓展了POMs在酶固定化领域的应用.Five Dawson-type polyoxometalate(POM)-based organic-inorganic hybrids,namely,[Ni(H_(2)biim)_(3)]_(4)·[Ni(H_(2)biim)_(2)(P_(2)W_(18)O_(62))_(2)]·2H_(2)O(1),[Co^(Ⅲ)(H_(2)biim)_(3)]_(2)[P_(2)W_(18)O_(62)]·8H_(2)O(2),[Cu(H_(2)biim)_(2)]_(3)[P_(2)W_(18)O_(62)]·4H_(2)O(3),[Co^(Ⅱ)(H_(2)biim)_(3)]_(2)H_(2)[P_(2)W_(18)O_(62)]·9H_(2)O(4)and[Ni(H_(2)biim)_(3)]_(3)[P_(2)W_(18)O_(62)]·2H_(2)O(5),were constructed from transition metal-biimidazole(TM-H_(2)biim)coordination cations and tungstophosphate polyoxoainons through hydrothermal and direct precipitation methods,and characterized by single crystal X-ray diffraction analysis,infrared(IR)spectroscopy and thermogravimetry-differential thermal analysis(TG-DTA).Compounds 1—5 were used as the supports for immobilizing horseradish peroxidase(HRP),exhibiting high load capacities.In addition,the reusability,storage stability and the performance for detecting hydrogen peroxide(H_(2)O_(2))of the obtained immobilized enzymes HRP/1—HRP/5 were also evaluated by circular dichroism(CD)spectroscopy and laser scanning confocal microscopy(LSCM).The experimental results show that the immobilization of HRP on POMs can be realized by the simple physical adsorption method.There is a strong interaction between POM and HRP,and the HRP immobiliza tion by POM not only improves the tolerance of HRP to the operation and storage environment,but also expands th application of POMs in the field of enzyme immobilization.

关 键 词：Dawson型钨磷酸盐 金属-联咪唑配合物 辣根过氧化物酶 酶固定化 过氧化氢检测 

分 类 号：O614.6[理学—无机化学]