Issue 9, 2023

Dual-ligand-functionalized dodeca-nuclear lanthanide–tungsten-cluster incorporated selenotungstates and fluorescence detection of dipicolinic acid (an anthrax biomarker)

Abstract

A series of rigid–flexible-ligand functionalized dodeca-nuclear lanthanide–tungsten heterometal cluster incorporated ring-shaped selenotungstates [H2N(CH3)2]16Na2[Ln4(H2O)6(HPZDA)2(HFMA)2W8O21][B-α-SeW9O33]4·29H2O [Ln = Ce3+ (1), Pr3+ (2), Nd3+ (3); H2PZDA = 2,3-pyrazine dicarboxylic acid, H2FMA = fumaric acid] and [H2N(CH3)2]14Cs2Na2[Eu4(H2O)6(HPZDA)2(HFMA)2W8O21][B-α-SeW9O33]4·30H2O (4) were prepared by a cooperative strategy of rigid and flexible ligands. The polyanion skeletons of 1–4 comprise an inorganic–organic hybrid dodeca-nuclear [Ln4(H2O)6(HPZDA)2(HFMA)2W8O21]14+ heterometallic cluster surrounded by four trivacant Keggin [B-α-SeW9O33]8− subunits in a rectangle-like arrangement. Based on its fluorescence properties, 4 was used as a fluorescent probe for detecting an anthrax biomarker dipicolinic acid (DPA) with a low limit of detection, and excellent selectivity and anti-interference. The possible fluorescence enhancement mechanism of 4 in the process of detecting DPA may stem from energy transfer from DPA to Eu3+ ions in 4, which can be confirmed by decay lifetime measurements of 4 in H2O and D2O with and without DPA, and a positive signal of the partial substitution of H2O ligands on Eu3+ ions by DPA ligands. This work proposes a feasible cooperative strategy of rigid and flexible ligands for constructing new structural types of polyoxometalate hybrids, and also provides some meaningful insights into efficient biomolecule detection by utilizing polyoxometalate-based luminescence materials.

Graphical abstract: Dual-ligand-functionalized dodeca-nuclear lanthanide–tungsten-cluster incorporated selenotungstates and fluorescence detection of dipicolinic acid (an anthrax biomarker)

Supplementary files

Article information

Article type
Research Article
Submitted
24 Febr. 2023
Accepted
01 Apr. 2023
First published
04 Apr. 2023

Inorg. Chem. Front., 2023,10, 2799-2810

Dual-ligand-functionalized dodeca-nuclear lanthanide–tungsten-cluster incorporated selenotungstates and fluorescence detection of dipicolinic acid (an anthrax biomarker)

T. Gong, S. Yang, Z. Wang, M. Li, S. Zhang, J. Liu, L. Chen and J. Zhao, Inorg. Chem. Front., 2023, 10, 2799 DOI: 10.1039/D3QI00361B

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