Nicotinic-Acid-Ornamented Tetrameric Rare-Earth-Substituted Phospho(III)tungstates with the Coexistence of Mixed Keggin/Dawson Building Blocks and Its Honeycomb Nanofilm for Detecting Toxins.

Abstract

A fascinating class of nicotinic-acid-ornamented tetrameric rare-earth (RE)-substituted phospho(III)tungstates [NH2(CH3)2]10Na4H8[RE2(NA)(HNA)(H2O)6(W2O4)(β-H2P2IIIW13O49)(α-HPIIIW9O33)]2·22 H2O [RE = Nd3+ (1-Nd), Tb3+ (2-Tb), Dy3+ (3-Dy), Ho3+ (4-Ho), HNA = nicotinic acid] were isolated through a one-step reaction method of Na2WO4·2H2O, H3PO3, HNA, NH2(CH3)2·HCl, and RE(NO3)·6H2O. Of meticulous concern is that HPO32- was used as a template to construct tetrameric RE-substituted phospho(III)tungstates including mixed heteropolyoxotungstate building blocks. Their hybrid polyoxoanions are composed of two symmetrical [RE2(NA)(HNA)(H2O)6(W2O4)(β-H2P2IIIW13O49)(α-HPW9O33)]11- units linked by RE-O-W bonds. The symmetrical unit consists of one peculiar heterometal nicotinic-acid-ornamented [RE2(NA)(HNA)(W2O4)]9+ cluster connecting a pentavacant Dawson-like [β-H2P2W13O49]12- and a trivacant Keggin [α-HPW9O33]8- subunits. Furthermore, dimethyldioctadecylammonium chloride (DMDODA·Cl) was used to combine with 1-Nd in the CHCl3-H2O system through electrostatic interactions, leading to the 1-Nd@DMDODA composite material. The honeycomb-patterned film of the 1-Nd @DMDODA composite material was successfully constructed by using the breath figure method on a glassy carbon electrode, which can offer abundant binding sites to Au nanoparticles (nano-Au). Ulteriorly, Au-functionalized 1-Nd@DMDODA-modified electrode was utilized as an electrochemical sensor to detect ochratoxin A, showing a good detection limit of 1.19 pM.