Circumventing the impact of agrochemicals on aquatic environments has become a necessity for health and ecological reasons. Herein, we report the use of a family of five eco-friendly water-stable isoreticular metal–organic frameworks (MOFs), prepared from amino acids, as adsorbents for the removal of neonicotinoid insecticides (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) from water. Among them, the three MOFs containing thioether-based residues show remarkable removal efficiency. In particular, the novel multivariate MOF {Sr II Cu II 6 [( S,S )-methox] 1.5 [( S,S )-Mecysmox] 1.50 (OH) 2 (H 2 O)}·36H 2 O ( 5 ), featuring narrow functional channels decorated with both −CH 2 SCH 3 and −CH 2 CH 2 SCH 3 thioalkyl chains—from l -methionine and l -methylcysteine amino acid-derived ligands, respectively—stands out and exhibits the higher removal efficiency, being capable to capture 100% of acetamiprid and thiacloprid in a single capture step under dynamic solid-phase extraction conditions—less than 30 s. Such unusual combination of outstanding efficiency, high stability in environmental conditions, and low-cost straightforward synthesis in 5 places this material among the most attractive adsorbents reported for the removal of this type of contaminants.
The exact chemical structure of non–crystallising natural products is still one of the main challenges in Natural Sciences. Despite tremendous advances in total synthesis, the absolute structural determination of a myriad of natural products with very sensitive chemical functionalities remains undone. Here, we show that a metal–organic framework (MOF) with alcohol–containing arms and adsorbed water, enables selective hydrolysis of glycosyl bonds, supramolecular order with the so–formed chiral fragments and absolute determination of the organic structure by single–crystal X–ray crystallography in a single operation. This combined strategy based on a biomimetic, cheap, robust and multigram available solid catalyst opens the door to determine the absolute configuration of ketal compounds regardless degradation sensitiveness, and also to design extremely–mild metal–free solid–catalysed processes without formal acid protons.
The search for efficient technologies empowering the selective capture of environmentally harmful heavy metals from wastewater treatment plants, at affordable prices, attracts wide interest but constitutes an important technological challenge. We report here an eco-friendly single-walled carbon nanotube buckypaper (SWCNT-BP) enriched with a multivariate amino acid-based metal–organic framework (MTV-MOF) for the efficient and selective removal of Pb 2+ in multicomponent water systems. Pristine MTV-MOF was easily immobilized within the porous network of entangled SWCNTs, thus obtaining a stable self-standing adsorbing membrane filter ( MTV-MOF/SWCNT-BP ). SWCNT-BP alone shows a moderately good removal performance with a maximum adsorption capacity of 180 mg·g –1 and a considerable selectivity for Pb(II) ions in highly concentrated multi-ion solutions over a wide range of lead concentration (from 200 to 10000 ppb). Remarkably, these features were outperformed with the hybrid membrane filter MTV-MOF/SWCNT-BP , exhibiting enhanced selectivity and adsorption capacity (310 mg·g –1 , which is up to 42% higher than that of the neat SWCNT-BP) and consequently enabling a more efficient and selective removal of Pb 2+ from aqueous media. MTV-MOF/SWCNT-BP was able to reduce [Pb 2+ ] from the dangerous 1000 ppb level to acceptable limits for drinking water, below 10 ppb, as established by the current EPA and WHO limits. Thus, the eco-friendly composite MTV-MOF/SWCNT-BP shows the potential to be effectively used several times as a reliable adsorbent for Pb 2+ removal for household drinking water or in industrial treatment plants for water and wastewater lead decontamination.
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