Department of Chemistry, Panjab University, Sector-14, Chandigarh-160014, India.
Department of Zoology, Panjab University, Sector-14, Chandigarh-160014, India.
Analyst. 2023 May 30;148(11):2582-2593. doi: 10.1039/d3an00469d.
Diethyl cyanophosphonate (DCNP), a simulant of Tabun, is a common pollutant in pharmaceutical waste and poses a high risk to living organisms. Herein, we demonstrate a compartmental ligand-derived trinuclear zinc(II) cluster [Zn(LH)(CHCOO)] as a probe for the selective detection and degradation of DCNP. It consists of two pentacoordinated Zn(II) [4.4.3.0]tridecane cages bridged through a hexacoordinated Zn(II) acetate unit. The structure of the cluster has been elucidated by spectrometric, spectroscopic, and single-crystal X-ray diffraction studies. The cluster shows a two-fold increased emission as compared to the compartmental ligand (at = 370 nm and = 463 nm) due to the chelation-enhanced fluorescence effect and acts as a turn-off signal in the presence of DCNP. It can detect DCNP at nano levels up to 186 nM (LOD). The direct bond formation between DCNP and Zn(II) the -CN group degrades it to inorganic phosphates. The mechanism of the interaction and degradation is supported by spectrofluorimetric experiments, NMR titration (H and P), time of flight mass spectrometry and density functional theory calculations. The applicability of the probe has been further tested by the bio-imaging of zebrafish larvae, analysis of high-protein food products (meat and fish) and vapour phase detection by paper strips.
二乙氰膦酸酯（DCNP）是塔崩的模拟物，是药物废物中的常见污染物，对生物体构成高度风险。在此，我们展示了一种隔室配体衍生的三核锌（II）簇 [Zn(LH)(CHCOO)]，作为选择性检测和降解 DCNP 的探针。它由两个通过六配位的 Zn(II) 乙酸盐单元桥接的五配位 Zn(II) [4.4.3.0]十三烷笼组成。通过光谱、光谱和单晶 X 射线衍射研究阐明了该簇的结构。与隔室配体相比，该簇的发射强度增加了两倍（在 = 370 nm 和 = 463 nm 处），这是由于螯合增强荧光效应，并且在存在 DCNP 时充当关闭信号。它可以在纳摩尔水平检测到 DCNP，最低检测限为 186 nM。DCNP 与 Zn(II) 的直接键合 破坏了 -CN 基团，将其降解为无机磷酸盐。相互作用和降解的机制得到了荧光光谱实验、NMR 滴定（H 和 P）、飞行时间质谱和密度泛函理论计算的支持。该探针的适用性已通过斑马鱼幼虫的生物成像、高蛋白食品（肉类和鱼类）的分析以及纸带气相检测进一步测试。
