Antimonotungstate-Based Heterometallic Framework Formed by the Synergistic Strategy of In Situ-Generated Krebs-Type Building Units and the Substitution Reaction and Its High-Efficiency Biosensing KRAS Gene

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Pub Date : 2024-12-31 DOI:10.1021/acs.inorgchem.4c04589

Peijun Gong, Yanying Wang, Junwei Zhao, Guo-Yu Yang

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Abstract

A novel antimonotungstate (AT)-based heterometallic framework {[Er(H₂O)₆]₂[Fe₄(H₂pdc)₄(B-β-SbW₉O₃₃)₂]}·50H₂O (1, H₂pdc = pyridine-2,5-dicarboxylic acid) was obtained through a synergistic strategy of in situ-generated transition-metal-encapsulated polyoxometalate (POM) building units and the substitution reaction. Its structural unit is composed of a tetra-Fe^III-substituted Krebs-type [Fe₄(H₂pdc)₄(B-β-SbW₉O₃₃)₂]^6– subunit and two [Er(H₂O)₆]³⁺ cations. This subunit can be regarded as a product of carboxylic oxygen atoms of H₂pdc ligands replacing active water ligands in the [Fe₄(H₂O)₁₀(B-β-SbW₉O₃₃)₂]^6– species. Apparently, the substitution action of carboxylic oxygen atoms of H₂pdc ligands for active water ligands, together with the coordination function of Er³⁺ ions, plays a connection role in the architecture of the three-dimensional (3-D) heterometallic framework. Based on the stability and high redox activity of 1, a glassy carbon electrode modified by 1 is used for the construction of an electrochemical biosensor (ECBS). Thus, such 1-based ECBS can sensitively detect the KRAS gene (a key genetic marker for identifying the occurrence of malignant tumors) and displays a low detection limit (0.106 pM), high selectivity, and reproducibility. This work not only provides a feasible approach to prepare novel multicomponent POM-based heterometallic frameworks but also establishes a new platform for biosensing the KRAS gene and extends the application scope of POM-based functional materials.

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原位生成的krebs型构建单元与取代反应协同形成的反单钨酸盐基异金属骨架及其高效生物传感KRAS基因

通过原位生成的过渡金属包封多金属氧酸盐（POM）构建单元和取代反应的协同策略，得到了一种新型的反单钨酸盐（AT）基异金属骨架{[Er(H2O)6]2[Fe4(H2pdc)4(B-β-SbW9O33)2]}·50H2O （1,h2pdc =吡啶-2,5-二羧酸）。它的结构单元由一个四- feii取代的krebs型[Fe4(H2pdc)4(B-β- sbw9o33)2]6 -亚基和两个[Er(H2O)6]3+阳离子组成。该亚基可以看作H2pdc配体的羧基氧原子取代[Fe4(H2O)10(B-β- sbw9o33)2]6 -中的活性水配体的产物。显然，H2pdc配体的羧基氧原子对活性水配体的取代作用，以及Er3+离子的配位作用，在三维异质金属框架的结构中起着连接作用。基于1的稳定性和高氧化还原活性，将1修饰的玻碳电极用于构建电化学生物传感器（ECBS）。因此，这种基于1的ECBS可以灵敏地检测KRAS基因（鉴别恶性肿瘤发生的关键遗传标记），且检测限低（0.106 pM），选择性高，重复性好。本研究不仅为制备新型多组分pom异质金属骨架提供了可行途径，而且为KRAS基因的生物传感搭建了新的平台，拓展了pom基功能材料的应用范围。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.