Toledo-Jaldin Helen Paola, Pinzón-Vanegas Cristian, Blanco-Flores Alien, Zamora-Moreno Julio, Rosales-Vázquez Luis D, Vilchis-Nestor Alfredo R, Reyes-Domínguez Iván A, Romero-Solano Miguel Á, Dorazco-González Alejandro
Autonomous University of San Luis Potosi, Institute of Metallurgy, San Luis Potosi, 78210, Mexico; National Technological of Mexico, Technological of Superior Studies of Tianguistenco, Mechanical Engineering Division, Tenango-La Marquesa Km22, Santiago Tilapa, 52650, Santiago Tianguistenco, Mexico.
Institute of Chemistry, National Autonomous University of Mexico, Mexico City, 04510, Mexico.
Environ Pollut. 2024 Feb 15;343:123195. doi: 10.1016/j.envpol.2023.123195. Epub 2023 Dec 22.
Organophosphorus pesticides (OPPs) such as parathion have extensive uses in agriculture and household applications. Chronic exposure to these pesticides can cause severe health and environmental issues. Therefore, a current ecological concern is associated with accumulating these noxious OPPs in food and water sources. In this work, a new Tb-doped Zn-LMOF (Zn-LMOF= (3D) {[Zn(1,4 benzenedicarboxylate)(EtOH)]·(EtOH)0.6}) was synthesized by a solvent-free reaction between the Zn-LMOF and the salt TbCl6HO using a high-speed ball milling. The Tb@Zn-LMOF was thoroughly characterized by multiple spectroscopic tools, including Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy, and studied in-depth as a luminescent sensor for a series of pesticides (parathion, malathion, methalaxil, carbofuran, iprodione, captan and glyphosate) in aqueous methanol. The Tb@Zn-LMOF is a long-lived green-emitting compound with luminescence originated by an efficient antenna effect from the excited energy levels of Zn-LMOF toward the 5D state of Tb ions, as it is displayed by its strong emission bands at 488, 545, 585, and 620 nm and a lifetime of 1.01 ms upon excitation at 290 nm. Additions of pesticides to a neutral methanolic dispersion of Tb@Zn-LMOF modified its green emission intensity with a pronounced selectivity toward parathion within the micromolar concentration range. The detection limit for parathion was calculated to be 3.04 ± 0.2 μM for Tb@Zn-LMOF. Based on P NMR and mass spectrometry studies, it is attributed to the release of lanthanide ions from Tb@Zn-LMOF with the simultaneous formation of a Tb-parathion complex.
对硫磷等有机磷农药（OPPs）在农业和家庭应用中有广泛用途。长期接触这些农药会导致严重的健康和环境问题。因此，当前一个生态问题是这些有害的有机磷农药在食物和水源中的积累。在这项工作中，通过高速球磨法，使Zn-LMOF（Zn-LMOF = (3D) {[Zn(1,4-苯二甲酸酯)(乙醇)]·(乙醇)0.6}）与盐TbCl₆·H₂O进行无溶剂反应，合成了一种新型的掺Tb的Zn-LMOF。通过多种光谱工具对Tb@Zn-LMOF进行了全面表征，包括带有能量色散X射线光谱的扫描电子显微镜，并对其作为甲醇水溶液中一系列农药（对硫磷、马拉硫磷、甲霜灵、克百威、异菌脲、克菌丹和草甘膦）的发光传感器进行了深入研究。Tb@Zn-LMOF是一种长寿命的绿色发光化合物，其发光源于从Zn-LMOF的激发能级到Tb离子的⁵D态的高效天线效应，这通过其在488、545、585和620 nm处的强发射带以及在290 nm激发下1.01 ms的寿命得以体现。向Tb@Zn-LMOF的中性甲醇分散体中添加农药会改变其绿色发射强度，在微摩尔浓度范围内对对硫磷具有明显的选择性。对于Tb@Zn-LMOF，对硫磷的检测限计算为3.04±0.2 μM。基于³¹P核磁共振和质谱研究，这归因于Tb@Zn-LMOF中镧系离子的释放以及同时形成的Tb-对硫磷络合物。
