Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, China.
Inorg Chem. 2022 Jul 18;61(28):10965-10976. doi: 10.1021/acs.inorgchem.2c01682. Epub 2022 Jul 6.
Two particular fumaric acid bridging lanthanide-encapsulated selenotungstates [HN(CH)]Na[Ln(HO)] [WO(CHO) (CHO)][SeWO][B-α-SeWO]·46HO [Ln = Ce (), La ()] were acquired by the deliberately designed step-by-step synthetic strategy, which are composed of four trilacunary Keggin [B-α-SeWO] and two original [SeWO] building units together with one fumaric acid bridging heterometallic [Ln(HO)][WO(CHO) (CHO)] entity. Particularly, this heterometallic cluster contains four fumaric acid ligands, which play two different roles: one works as the pendant decorating the cluster and the other acts as the linker connecting the whole structure. In addition, the hybrid material was produced through the cation exchange of and dimethyl distearylammonium chloride (DDA·Cl) and its beehive-shaped film of was prepared by the breath figure method, which can be further used to establish an electrochemical biosensor for detecting a kind of mycotoxin-ochratoxin A (OX-A). The beehive-shaped film-based electrochemical biosensor exhibits good reproducibility and specific sensing toward OX-A with a low detection limit of 29.26 pM. These results highlight the huge feasibility of long-chain flexible ligands in building lanthanide-encapsulated selenotungstates with structural complexity and further demonstrate great electrochemical application potentiality of polyoxometalate-involved materials in bioanalysis, tumor diagnosis, and iatrology.
两种特殊的富马酸桥连镧系元素封装的硒钨酸盐 [HN(CH)]Na[Ln(HO)] [WO(CHO) (CHO)][SeWO][B-α-SeWO]·46H 2 O [Ln = Ce (), La ()] 通过精心设计的逐步合成策略获得,它们由四个三聚体 Keggin [B-α-SeWO] 和两个原始 [SeWO] 构建单元以及一个富马酸桥连杂金属 [Ln(HO)][WO(CHO) (CHO)] 实体组成。特别地,这个杂金属簇含有四个富马酸配体,它们发挥了两种不同的作用:一个作为支链修饰簇,另一个作为连接整个结构的链接。此外,通过阳离子交换制备了 和二甲基硬脂基氯化铵 (DDA·Cl) 的杂化材料,并通过呼吸图案法制备了其蜂窝状薄膜,可进一步用于建立电化学生物传感器来检测一种真菌毒素-赭曲霉毒素 A (OX-A)。基于 蜂窝状薄膜的电化学生物传感器对 OX-A 表现出良好的重现性和特异性,检测限低至 29.26 pM。这些结果突出了长链柔性配体在构建具有结构复杂性的镧系元素封装硒钨酸盐方面的巨大可行性,并进一步证明了多金属氧酸盐材料在生物分析、肿瘤诊断和医学中的电化学应用潜力。