There is a need to develop low-cost, reliable and portable devices to enhance the efficiency of microextraction techniques in complex samples. Metal-organic frameworks (MOFs) have proven to be promising sorbents due to their well-documented properties. However, their green preparation and combination with paper-based substrates have not been satisfactorily explored to fabricate sustainable sorptive phases. In this work, the hybridization of a paper substrate (as a sustainable support) with MOFs (as a sorptive phase) was carried out by one-pot approach. Concretely, the selected MOF, MIL-53(Al), was growth onto the paper surface in aqueous solution without the need for high temperature or pressure, thereby aligning with the Green Analytical Chemistry principles. The optimized composite (MIL-53(Al)@cellulose paper) was characterized and evaluated as extraction sorbent for five neonicotinoids (NEOs) (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid). Furthermore, its feasibility was demonstrated by isolating these pollutants from environmental water samples, followed their determination by HPLC coupled to diode array detection. The whole method showed satisfactory analytical performance with recoveries between 86 and 114 %, suitable precision (with RSD lower than 14 %), and limits of detection ranged from 1.0 to 1.6 μg L. Besides, the greenness of the method was assessed by application of different existing metrics. The developed extraction device was affordable (<0.08 €/device) and mechanical and chemically stable, being possible its reuse more than 11 cycles, thus demonstrating its suitability for rapid screening of pesticides in environmental samples. This report presents, for the first time, the green synthesis of MIL-53(Al)cellulose paper composite and its application as a sorptive phase for the extraction of NEOs from environmental water samples. We believe that the proposed strategy for fabricating these sustainable paper-based sorptive phases paves the way for further hybridizations with other MOFs or materials. Additionally, it opens up large possibilities for their application in extraction of pollutants or other hazardous compounds in aquatic environments.

中文翻译：

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绿色合成MIL53(Al)改性纸基分析装置，用于从环境水样中高效提取新烟碱类杀虫剂


需要开发低成本、可靠且便携式的设备来提高复杂样品中微萃取技术的效率。金属有机框架（MOF）因其具有充分记录的特性而被证明是有前途的吸附剂。然而，它们的绿色制备以及与纸基基材的结合尚未得到令人满意的探索以制造可持续的吸附相。在这项工作中，纸质基材（作为可持续支撑）与 MOF（作为吸附相）的杂交是通过一锅法进行的。具体而言，所选的 MOF MIL-53(Al) 在水溶液中生长到纸张表面，无需高温或高压，从而符合绿色分析化学原理。优化的复合材料（MIL-53（Al）@纤维素纸）作为五种新烟碱类（NEO）（噻虫嗪、噻虫胺、吡虫啉、啶虫脒和噻虫啉）的提取吸附剂进行了表征和评估。此外，通过从环境水样中分离这些污染物，然后通过 HPLC 结合二极管阵列检测对其进行测定，证明了其可行性。整个方法分析性能良好，回收率在86%~114%之间，精密度合适（RSD低于14%），检出限在1.0~1.6μg·L之间。此外，通过应用评价方法的绿色度。不同的现有指标。所开发的提取装置价格实惠（<0.08 欧元/装置）且机械和化学稳定，可重复使用超过 11 个周期，从而证明其适用于快速筛查环境样品中的农药。 该报告首次介绍了 MIL-53(Al) 纤维素纸复合材料的绿色合成及其作为吸附相从环境水样中提取 NEO 的应用。我们相信，所提出的制造这些可持续纸基吸附相的策略为与其他 MOF 或材料的进一步杂交铺平了道路。此外，它还为其在水生环境中污染物或其他有害化合物的提取中的应用开辟了巨大的可能性。