The development of polyoxometalate chemistry not only is derived from the continuous discovery of novel polyoxometalates (POMs) but also stems from the exploitation of their new functionalities. In this work, we obtained a rigid sulfur-containing heterocyclic ligand-linking aggregate [N(CH₃)₄]₁₀Na₆H₆[Ce₈(H₂O)₂₆W₈(HTDA)₂(TDA)₂O₂₀][SeW₄O₁₈]₂[SeW₉O₃₃]₄·112H₂O (1) (H₂TDA = 2,5-thiophenedicarboxylic acid). Its polyanionic unit consists of one [Ce₄(H₂O)₁₃W₄O₁₀(HTDA)(TDA)O₁₀]¹⁸⁺ cluster and two kinds of Keggin-type [SeW₄O₁₈] and [SeW₉O₃₃] segments. It is noteworthy that H₂TDA ligands not only work as connectors to link two symmetrical {[Ce₄(H₂O)₁₃W₄(HTDA)(TDA)O₁₀][SeW₄O₁₈][SeW₉O₃₃]₂}^11– units but also function as ornaments to graft to the polyanionic backbone. Furthermore, 1 and 3,4-ethylenedioxythiophene (EDOT) were deposited on the glassy carbon electrode (GCE) by the electropolymerization (EPM) method, resulting in a 1-poly(3,4-ethylenedioxythiophene) (1-PEDOT) composite film, which can provide sufficient binding sites to immobilize Au nanoparticles (Au NPs). Hereafter, the Au NPs-immobilized 1-PEDOT modified electrode (Au/1-PEDOT/GCE) was used to construct an electrochemical aptasensor to detect mucin 1, showing a low detection limit of 29.5 fM in the Tris solution. This work not only demonstrates that rigid heterocyclic ligands are beneficial for the creation of novel rare-earth-substituted selenotungstate hybrids but also provides more enlightenment for POM-based materials used for electrochemical detection of cancer markers.

中文翻译：

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2,5-噻吩二甲酸桥联六聚CeIII取代的硒钨酸盐及其在检测粘蛋白1中的应用

多金属氧酸盐化学的发展不仅源于新型多金属氧酸盐（POM）的不断发现，而且源于对其新功能的开发。在这项工作中，我们获得了刚性含硫杂环配体连接聚集体[N(CH ₃ ) ₄ ] ₁₀ Na ₆ H ₆ [Ce ₈ (H ₂ O) ₂₆ W ₈ (HTDA) ₂ (TDA) ₂ O ₂₀ ][SeW ₄ O ₁₈ ] ₂ [SeW ₉ O ₃₃ ] ₄ ·112H ₂ O ( 1 ) (H ₂ TDA = 2,5-噻吩二甲酸)。其聚阴离子单元由1个[Ce ₄ (H ₂ O) ₁₃ W ₄ O ₁₀ (HTDA)(TDA)O ₁₀ ] ¹⁸⁺簇和两种Keggin型[SeW ₄ O ₁₈ ]和[SeW ₉ O ₃₃ ] 段。值得注意的是，H ₂ TDA配体不仅作为连接体连接两个对称的{[Ce ₄ (H ₂ O) ₁₃ W ₄ (HTDA)(TDA)O ₁₀ ][SeW ₄ O ₁₈ ][SeW ₉ O ₃₃ ] ₂ } ^11–单元也可作为接枝到聚阴离子主链上的装饰物。此外，通过电聚合（EPM）方法将1和3,4-乙撑二氧噻吩（EDOT）沉积在玻碳电极（GCE）上，得到1-聚（3,4-乙撑二氧噻吩）（1 -PEDOT）复合薄膜。 ，它可以提供足够的结合位点来固定金纳米粒子（Au NPs）。此后，使用Au NPs固定的1 -PEDOT修饰电极（Au/ 1 -PEDOT/GCE）构建电化学适体传感器来检测粘蛋白1，在Tris溶液中显示出29.5 fM的低检测限。这项工作不仅证明了刚性杂环配体有利于新型稀土取代硒钨酸盐杂化物的制备，而且为基于POM的材料用于癌症标志物的电化学检测提供了更多启示。