Grancha Thais, Garcia-Atienza Patricia, Armenta Sergio, Herrero-Martínez José Manuel, Percoco Rita Maria, Armentano Donatella, Ferrando-Soria Jesús, Pardo Emilio
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia 46980 Paterna Valencia Spain
Departamento de Química Analítica, Universitat de València, c/Dr Moliner, 50 46100 Burjassot Valencia Spain
J Mater Chem A Mater. 2025 May 19. doi: 10.1039/d5ta01530h.
The presence of residues of drugs of abuse in potable water is a growing concern worldwide. Different studies have detected traces of opioids, cocaine, amphetamines, or cannabinoids in surface water, groundwater, and even treated drinking water, which is a clear indicator of insufficient removal during wastewater treatment processes. These substances may persist in the environment, posing potential long-term risks to human health and ecosystems, and consequently, making the quest for efficient decontamination technologies mandatory. Herein, we explore the use of a family of six eco-friendly water-stable isoreticular metal-organic frameworks (MOFs) and multivariate MOFs (MTV-MOFs), prepared from amino acids, as adsorbents for the removal of a mix of 29 drugs of abuse from water. Among them, the MOF prepared from the natural amino acid l-methionine, with the formula {CaCu (,)-methox(HO)}·16HO (3), features channels densely decorated with thioalkyl (-CHCHSCH) residues and exhibits an outstanding removal efficiency being capable to remove them almost completely in a single capture step under dynamic solid-phase extraction conditions (less than 30 seconds). Also, the removal performance of 3 toward the highly concerning drug fentanyl -responsible for a large number of deaths due to overdose in the United States and Canada was further investigated. 3 is capable of capturing fentanyl entirely, for at least 16 consecutive cycles, outperforming the current reference material, powdered activated carbon (PAC). Finally, the crystal structures of two host-guest adsorbates with amphetamine molecules embedded within the channels of two of the MOFs of the family {SrCu (,)-mecysmox(HO)}·15HO (2') and (3) could be resolved, helping to unveil the interactions between the drugs and the MOF matrix. Moreover, the crystal structure of another host-guest adsorbate with fentanyl molecules hosted in MOF SrCu (,)-methox(HO)}·16HO (3') was also elucidated. Overall, these properties situate MOF 3 among the most attractive adsorbents for the challenging removal of such emerging pollutants and it is a viable alternative for application in a real-world environment.
饮用水中存在滥用药物的残留，这一问题在全球范围内日益受到关注。不同的研究在地表水、地下水甚至经过处理的饮用水中都检测到了阿片类药物、可卡因、苯丙胺或大麻素的痕迹，这清楚地表明废水处理过程中的去除效果不佳。这些物质可能会在环境中持续存在，对人类健康和生态系统构成潜在的长期风险，因此，寻求高效的净化技术势在必行。在此，我们探索使用一族六种由氨基酸制备的环境友好型水稳定等规金属有机框架材料（MOF）和多元MOF（MTV-MOF）作为吸附剂，用于从水中去除29种滥用药物的混合物。其中，由天然氨基酸L-甲硫氨酸制备的MOF，化学式为{CaCu (,)-甲氧基(HO)}·16HO（3），其通道被硫代烷基（-CHCHSCH）残基密集修饰，在动态固相萃取条件下（不到30秒），单次捕获步骤就能几乎完全去除这些药物，展现出卓越的去除效率。此外，还进一步研究了3对备受关注的药物芬太尼的去除性能，芬太尼在美国和加拿大导致了大量过量用药死亡事件。3能够连续至少16个循环完全捕获芬太尼，性能优于当前的参考材料粉末活性炭（PAC）。最后，解析了两种主客体吸附物的晶体结构，其中苯丙胺分子嵌入了该族中两种MOF{SrCu (,)-甲氧基肟(HO)}·15HO（2'）和（3）的通道内，这有助于揭示药物与MOF基质之间的相互作用。此外，还阐明了另一种主客体吸附物的晶体结构，其中芬太尼分子存在于MOF SrCu (,)-甲氧基(HO)}·16HO（3'）中。总体而言，这些特性使MOF 3成为去除此类新兴污染物极具吸引力的吸附剂之一，是在实际环境中应用的可行替代方案。
