Environmental and Bio-Analytical Laboratories, Department of Chemistry, Sharif University of Technology, P.O. Box 11365-9516, Tehran, Iran.
Peptide Chemistry Research Institute, Department of Chemistry, K. N. Toosi University of Technology, P. O. Box 15875-4416, Tehran, Iran.
Anal Chim Acta. 2024 Feb 15;1290:342206. doi: 10.1016/j.aca.2024.342206. Epub 2024 Jan 2.
Attentions regarding ordered mesoporous silica materials (OMSs), with large specific surface areas and narrow pore size distribution, which are prepared via self-assembly techniques, have been raised in sorption, separation, and sample preparation. However, in order to extend and improve their applications, a functionalization step is required. Organic units can be anchored on the inner or outer surface as well as in the silica wall framework by co-condensation-, grafting-, and periodic mesoporous organosilica (PMO) preparation approaches. Apparently, by synthesizing PMO with extensive and flexible organic bridging groups within the mesoporous wall, an efficient extractive phase can be achieved.
We employed tyrosine amino acid to synthesize a PMO-based extractive phase. The FT-IR, H NMR, HR-ESI-MS, Low angle-XRD, TEM, FESEM, BET, and EDX-MAP analyses confirmed the successful synthesis of PMO within the salt-assisted templating method. A comprehensive study on sorption behavior of PMO was performed and its efficiency was evaluated against the grafting and co-condensation methods. Then, it was implemented to the pipette tip-micro solid phase extraction (PT-μ-SPE) of widely used non-steroidal anti-inflammatory drugs (NSAIDs) in water/wastewaters. Limits of detection and quantification were obtained in the range of 0.1-1.5 and 0.3-5 μg L, respectively. The calibration plots are linear in the 1-1000, 3-1000, 10-750, and 3-750 μg L, respectively. The intra-and inter-day precision at 50 and 200 μg L levels are 2.9-7.1 % and 3.5-8%, while recoveries are between 84 and 111 %.
High-capacity tyrosine functionalized PMO with 2D hexagonal symmetry silica mesoporous structures found to be highly efficient extractive media. Despite the bulkiness and flexibility of the bridging group within the mesoporous wall, the synthesis condition was optimized in order to load more organic content in the PMO structure. The PMO performance was superior over organically modified ordered mesoporous silica materials prepared by the grafting and co-condensation methods.
具有大比表面积和窄孔径分布的有序介孔硅材料（OMSs）通过自组装技术制备，在吸附、分离和样品制备方面受到了关注。然而，为了扩展和改进它们的应用，需要进行功能化步骤。有机单元可以通过共缩合、接枝和周期性介孔有机硅（PMO）制备方法固定在内表面或外表面以及二氧化硅壁骨架上。显然，通过在介孔壁内合成具有广泛和灵活的有机桥接基团的 PMO，可以获得有效的萃取相。
我们采用酪氨酸氨基酸合成了一种基于 PMO 的萃取相。FT-IR、H NMR、HR-ESI-MS、低角度-XRD、TEM、FESEM、BET 和 EDX-MAP 分析证实了 PMO 在盐辅助模板法中的成功合成。对 PMO 的吸附行为进行了全面研究，并将其效率与接枝和共缩合方法进行了评估。然后，将其应用于水/废水中广泛使用的非甾体抗炎药（NSAIDs）的微量固相萃取（PT-μ-SPE）。检测限和定量限分别在 0.1-1.5 和 0.3-5μg/L 的范围内。校准曲线在 1-1000、3-1000、10-750 和 3-750μg/L 的范围内均呈线性。在 50 和 200μg/L 水平的日内和日间精密度分别为 2.9-7.1%和 3.5-8%，回收率在 84-111%之间。
具有二维六方对称二氧化硅介孔结构的高容量酪氨酸功能化 PMO 被发现是高效的萃取介质。尽管介孔壁内桥接基团的体积大和灵活性，但为了在 PMO 结构中负载更多的有机含量，优化了合成条件。PMO 的性能优于通过接枝和共缩合方法制备的有机改性有序介孔硅材料。
