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An unprecedented dumbbell-shaped pentadeca-nuclear W-Er heterometal cluster stabilizing nanoscale hexameric arsenotungstate aggregate and electrochemical sensing properties of its conductive hybrid film-modified electrode

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Abstract

Cluster-based functional materials have made remarkable progress owing to their wonderful structures and distinctive physicochemical performances, one of on-going advancements of which is basically driven by synthetic chemistry of exploring and constructing novel nanosized gigantic polyoxometalate (POM) aggregates. In this article, an unprecedented nanoscale hexameric arsenotungstate aggregate Na9K16H4[Er0.5K0.5(H2O)7][Er5W10O26(H2O)14][B-α-AsW9O33]6·102H2O (1) has been synthesized by the combined synthetic strategy of simultaneously using the arsenotungstate precursor and simple tungstate material in a highly acidic aqueous solution. The {[Er5W10O26(H2O)14][B-α-AsW9O33]6}31− polyanion in 1 consists of an intriguing dumbbell-shaped pentadeca-nuclear W-Er heterometal {Er5W10O26(H2O)14}23+ cluster connecting six trilacunary [B-α-AsW9O33]9− moieties, which has never been seen previously. Furthermore, through electropolymerization of 1 and pyrrole on the conductive substrate, a thickness-controllable and robust 1-PPY (PPY = polypyrrole) hybrid film was successfully prepared, which represents the first POM-PPY film assembled from high-nuclear lanthanide (Ln) encapsulated POM and PPY hitherto. The 1-PPY film-based electrochemical biosensor exhibits a favorable recognition performance for ochratoxin A in multiple media. This work not only provides a feasible combined synthetic strategy of the POM precursor and simple tungstate material for constructing complicated multi-Ln-inserted POM aggregates, but also offers a promising electrochemical platform constructed from POM-based conductive films for identifying trace biomolecules in complex environments.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 21871077, 21671054, 21771052, 22071042, 22171070, 91122028, and 21831001) and the Program for Innovation Teams in Science and Technology in Universities of Henan Province (No. 20IRTSTHN004).

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  1. Dan Wang and Jun Jiang contributed equally to this work.

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

    Dan Wang, Jun Jiang, Meng-Ya Cao, Sai-Sai Xie, Ya-Min Li, Li-Juan Chen & Jun-Wei Zhao

  2. MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Guo-Yu Yang

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  1. Dan Wang
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Correspondence to Li-Juan Chen, Jun-Wei Zhao or Guo-Yu Yang.

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An unprecedented dumbbell-shaped pentadeca-nuclear W-Er heterometal cluster stabilizing nanoscale hexameric arsenotungstate aggregate and electrochemical sensing properties of its conductive hybrid film-modified electrode

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Wang, D., Jiang, J., Cao, MY. et al. An unprecedented dumbbell-shaped pentadeca-nuclear W-Er heterometal cluster stabilizing nanoscale hexameric arsenotungstate aggregate and electrochemical sensing properties of its conductive hybrid film-modified electrode. Nano Res. 15, 3628–3637 (2022). https://doi.org/10.1007/s12274-021-3940-8

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  • DOI: https://doi.org/10.1007/s12274-021-3940-8

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