Shandong Analysis and Test Center, Key Laboratory for Applied Technology of Sophisticated Analytical Instruments of Shandong Province, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, China.
School of Materia Medica, Hebei University of Chinese Medicine, No. 3 Xingyuan Lu, Shijiazhuang 050200, China.
ACS Appl Mater Interfaces. 2022 Jan 12;14(1):2102-2112. doi: 10.1021/acsami.1c22033. Epub 2021 Dec 30.
Composite adsorbents based on metal-organic frameworks (MOFs) are excellent candidates for solid-phase extraction (SPE) due to their diverse chemical functionality and multilevel porosity. MOF superstructures based on self-assembly at room temperature (RT) could have less energy consumption and easier manipulation due to the larger complex geometry. The π-π stacking of the benzene ring could not only enhance the interaction toward hydrophobic or plane-structured targets but also be expected to promote the formation of the MOF superstructure. In this work, in the established RT self-assembly synthesis system, several factors were investigated to see how to obtain functional MOF superstructures with a regular geometry, among which the number of benzene rings in the ligand was mainly tested for its impact on self-assembly and adsorption capacity. By means of adsorption experiments and computational fluid dynamics (CFD) simulation, the relationship between structure and activity (SARs) was further explored. Interestingly, the MOF unit with the lowest specific surface area performed the best in adsorption. Then, the selected functional MOF superstructure and ionic liquid were used to produce the composite paper membrane facilely applied in the SPE device. After optimization of the preparation conditions and operation parameters, the established SPE-HPLC-UV method could selectively analyze tetracycline-like antibiotics in the range of 16.6-833.3 ng/g (ppb) in a meat sample. This work provided an RT synthesis method to produce a microsize MOF superstructure, with experimental and theoretical insights into the SARs, which could be expanded in the design of other MOF-based SPE composite membranes toward one group of analogues.
基于金属-有机骨架（MOFs）的复合吸附剂由于其多样的化学功能和多层次的孔隙率，是固相萃取（SPE）的理想候选材料。基于室温（RT）自组装的 MOF 超结构由于具有较大的复杂几何形状，因此可能具有较低的能耗和更易于操作。苯环的π-π堆积不仅可以增强对疏水性或平面结构靶标的相互作用，而且有望促进 MOF 超结构的形成。在这项工作中，在已建立的 RT 自组装合成体系中，研究了几个因素，以了解如何获得具有规则几何形状的功能性 MOF 超结构，其中主要测试了配体中苯环的数量对自组装和吸附能力的影响。通过吸附实验和计算流体动力学（CFD）模拟，进一步探讨了结构与活性（SARs）之间的关系。有趣的是，比表面积最低的 MOF 单元在吸附方面表现最佳。然后，选择功能性 MOF 超结构和离子液体来制备复合纸膜，可轻松应用于 SPE 装置。在优化了制备条件和操作参数后，建立的 SPE-HPLC-UV 方法可以选择性地在 16.6-833.3 ng/g（ppb）的范围内分析肉样中的四环素类抗生素。这项工作提供了一种 RT 合成方法来制备微尺寸 MOF 超结构，并对 SARs 进行了实验和理论上的研究，这可以扩展到其他基于 MOF 的 SPE 复合膜的设计中，以针对一类类似物。
