In this work, computational and experimental methods were used to study the adsorption of estrogens and glucocorticoids on metal–organic frameworks (MOFs). Computer-aided molecular simulation was applied to predict the adsorption of eight analytes on four MOFs (MIL-101(Cr), MIL-100(Fe), MIL-53(Al), and UiO-66(Zr)) by examining molecular interactions and calculating free binding energies. Subsequently, the four water-stable MOFs were synthesized and evaluated as adsorbents for the target hormones in aqueous solution. As the MOF exhibiting the highest adsorption capacity in both computations and experiments, MIL-53(Al) was chosen as a sorbent to develop a dispersive micro-solid-phase extraction procedure coupled to ultra-performance liquid chromatography tandem mass spectrometry for simultaneous determination of the target analytes in water and human urine samples. Experimental parameters affecting the extraction recoveries, including pH, ionic strength, MIL-53(Al) amount, extraction time, desorption time, and desorption solvent, were optimized. The optimized method provided a linear range of 0.005025–368.6 μg/L with good correlation coefficients (0.9982 ≤ r² ≤ 0.9992), and limits of detection (S/N = 3) and quantification (S/N = 10) of 0.0015–1.0 μg/L and 0.005–1.8 μg/L, respectively. The analyte recoveries were in the range of 80.6–98.4% in water samples and 88.4–93.2% in urine samples. Furthermore, MIL-53(Al) showed good stability over 10 extraction cycles (RSD < 10.0%). Good agreement between experimental measurements and computational results showed the potential of this approach for elucidating adsorption mechanisms and predicating extraction efficiencies for MOFs and targets, providing new directions for the development and utilization of MOFs.

在这项工作中，使用计算和实验方法研究了雌激素和糖皮质激素在金属有机骨架（MOF）上的吸附。应用计算机辅助分子模拟通过检查分子来预测四种MOF（MIL-101（Cr），MIL-100（Fe），MIL-53（Al）和UiO-66（Zr））上八种分析物的吸附相互作用并计算自由结合能。随后，合成了四种水稳定性MOF，并将其评估为目标激素在水溶液中的吸附剂。由于MOF在计算和实验中均表现出最高的吸附能力，MIL-53（Al）被选作吸附剂，以开发与超高效液相色谱串联质谱联用的分散微固相萃取程序，以同时测定水和人尿液样品中的目标分析物。优化了影响萃取回收率的实验参数，包括pH，离子强度，MIL-53（Al）含量，萃取时间，脱附时间和脱附溶剂。优化的方法提供了0.005025–368.6μg/ L的线性范围，具有良好的相关系数（0.9982≤[R ² ≤0.9992），和检测限（S / N = 3）和分别0.0015-1.0微克/升和0.005-1.8微克/升，量化（S / N = 10）。水样品中分析物的回收率在80.6–98.4％范围内，尿液样品中的分析物回收率在88.4–93.2％范围内。此外，MIL-53（Al）在10个萃取循环中表现出良好的稳定性（RSD <10.0％）。实验测量结果和计算结果之间的良好一致性表明，这种方法对于阐明MOF和靶标的吸附机理和预测提取效率的潜力，为MOF的开发和利用提供了新的方向。