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双三角锥{SeO}基团桥连的2-吡啶甲酸修饰的铈镶嵌多金属氧酸盐,包括用于电化学传感赭曲霉毒素A的混合硒钨酸盐亚基。

Double Trigonal Pyramidal {SeO} Groups Bridged 2-Picolinic Acid Modified Cerium-Inlaid Polyoxometalate Including Mixed Selenotungstate Subunits for Electrochemically Sensing Ochratoxin A.

作者信息

Liu Lulu, Jiang Jun, Cui Limin, Zhao Junwei, Cao Xinhua, Chen Lijuan

机构信息

Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, China.

Green Catalysis and Synthesis Key Laboratory of Xinyang City, College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang, Henan 464000, China.

出版信息

Inorg Chem. 2022 Jan 31;61(4):1949-1960. doi: 10.1021/acs.inorgchem.1c03103. Epub 2022 Jan 20.

Abstract

An organic-inorganic hybrid trigonal pyramidal {SeO} group, bridged cerium-inlaid polyoxometalate (POM) Na[SeCe(HO)W(HPIC)O][B-β-SeWO][SeWO]·60HO () (HPIC = 2-picolinic acid), containing two disparate selenotungstate (ST) building blocks was synthesized by a one-step assembly strategy, which is established by two asymmetric sandwich-type {[Ce(HO)W(HPIC)O][B-β-SeWO][SeWO]} moieties joined by double trigonal pyramidal {SeO} groups. Its outstanding structural trait is that it contains two types of ST building blocks, Keggin-type [B-β-SeWO] and Dawson-like [SeWO], which are extremely rare in ST chemistry. Remarkably, [SeWO] is first obtained in lanthanide-inlaid STs. Furthermore, @PPy conductive film (PPy = polypyrrole) was prepared by electrochemical polymerization and served as the electrode material, and then nano-gold particles (NGPs) were deposited on the surface of @PPy conductive film by an electrochemical deposition method in order to immobilize the aptamer of ochratoxin A. With the help of exonuclease I (EN I), the oxidation peak of the metalized Ag works as the detection signal to achieve the detection of ochratoxin A (OTXA). This study offers an available approach for creating organic-inorganic hybrid heteroatom-bridged lanthanide-inlaid POMs and reveals the likelihood of extending heteroatom-bridged lanthanide-inlaid POMs into electrochemical biosensing applications.

摘要

通过一步组装策略合成了一种有机-无机杂化三角锥型{SeO}基团桥连铈镶嵌多金属氧酸盐(POM)Na[SeCe(HO)W(HPIC)O][B-β-SeWO][SeWO]·60HO ()(HPIC = 2-吡啶甲酸),它包含两个不同的硒钨酸盐(ST)结构单元,由两个不对称夹心型{[Ce(HO)W(HPIC)O][B-β-SeWO][SeWO]}部分通过双三角锥型{SeO}基团连接而成。其突出的结构特点是它包含两种类型的ST结构单元,即Keggin型[B-β-SeWO]和类Dawson型[SeWO],这在ST化学中极为罕见。值得注意的是,[SeWO]首次在镧系镶嵌的STs中获得。此外,通过电化学聚合制备了@PPy导电膜(PPy = 聚吡咯)并用作电极材料,然后通过电化学沉积方法将纳米金颗粒(NGPs)沉积在@PPy导电膜表面以固定赭曲霉毒素A的适配体。在外切核酸酶I(EN I)的帮助下,金属化银的氧化峰作为检测信号实现对赭曲霉毒素A(OTXA)的检测。该研究为创建有机-无机杂化杂原子桥连镧系镶嵌POMs提供了一种可行的方法,并揭示了将杂原子桥连镧系镶嵌POMs扩展到电化学生物传感应用中的可能性。

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