Pesticides luminescent sensing by a Tb3+-doped Zn metal-organic framework with selectivity towards parathion.

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 Tb3+-doped Zn-LMOF (Zn-LMOF= (3D) {[Zn3(1,4 benzenedicarboxylate)3(EtOH)2]·(EtOH)0.6}∞) was synthesized by a solvent-free reaction between the Zn-LMOF and the salt TbCl3·6H2O 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 Tb3+ 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 31P NMR and mass spectrometry studies, it is attributed to the release of lanthanide ions from Tb@Zn-LMOF with the simultaneous formation of a Tb3+-parathion complex.

Water-soluble fluorescent chemosensor for sorbitol based on a dicationic diboronic receptor. Crystal structure and spectroscopic studies.

Selective recognition of saccharides by phenylboronic dyes capable of functioning in aqueous conditions is a central topic of modern supramolecular chemistry that impacts analytical sciences and biological chemistry. Herein, a new dicationic diboronic acid structure 11 was synthesized, structurally described by single-crystal X-ray diffraction, and studied in-depth as fluorescent receptor for six saccharides in pure water at pH = 7.4. This dicationic receptor 11 has been designed particularly to respond to sorbitol and involves two convergent and strongly acidified phenyl boronic acids, with a pKa of 6.6, that operate as binding sites. The addition of sorbitol in the micromolar concentration range to receptor 11 induces strong fluorescence change, but in the presence of fructose, mannitol, glucose, lactose and sucrose, only moderate optical changes are observed. This change in emission is attributed to a static complexation photoinduced electron transfer mechanism as evidenced by lifetime experiments and different spectroscopic tools. The diboronic receptor has a high affinity/selectivity to sorbitol (K = 31 800 M-1) over other saccharides including common interfering species such as mannitol and fructose. The results based on 1H, 11B NMR spectroscopy, high-resolution mass spectrometry and density functional theory calculations, support that sorbitol is efficiently bound to 11 in a 1 : 1 mode involving a chelating diboronate-sorbitol complexation. Since the experimental B⋯B distance (5.3 Å) in 11 is very close to the calculated distance from the DFT-optimized complex with sorbitol, the efficient binding is attributed to strong acidification and preorganization of boronic acids. These results highlight the usefulness of a new diboronic acid receptor with a strong ability for fluorescent recognition of sorbitol in physiological conditions.