背景:关于有序介孔二氧化硅材料(OMS)的注意事项,具有大的比表面积和窄的孔径分布,它们是通过自组装技术制备的,在吸附中提高了,分离,和样品制备。然而,为了扩展和改进它们的应用,需要官能化步骤。有机单元可以通过共缩合固定在内表面或外表面上以及二氧化硅壁框架中-,嫁接-,和周期性的中孔有机二氧化硅(PMO)制备方法。显然,通过在介孔壁内合成具有广泛而灵活的有机桥连基团的PMO,一个有效的萃取阶段可以实现。
结果:我们使用酪氨酸氨基酸来合成基于PMO的萃取相。FT-IR,1HNMR,HR-ESI-MS,低角度-XRD,TEM,FESEM,BET,和EDX-MAP分析证实了在盐辅助模板方法中成功合成了PMO。对PMO的吸附行为进行了全面研究,并根据接枝和共缩合方法评估了其效率。然后,它被应用于在水/废水中广泛使用的非甾体抗炎药(NSAIDs)的移液管尖端微固相萃取(PT-μ-SPE)。检测和定量的极限分别在0.1-1.5和0.3-5μgL-1的范围内。校准图分别在1-1000、3-1000、10-750和3-750μgL-1中是线性的。50和200μgL-1水平的日内和日间精确度分别为2.9-7.1%和3.5-8%,而回收率在84%到111%之间。
结论:发现具有2D六方对称二氧化硅介孔结构的高容量酪氨酸官能化PMO是高效提取介质。尽管中孔壁内的桥接基团庞大且灵活,优化了合成条件,以在PMO结构中负载更多的有机物含量。PMO性能优于通过接枝和共缩合方法制备的有机改性的有序介孔二氧化硅材料。
BACKGROUND: 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.
RESULTS: We employed tyrosine amino acid to synthesize a PMO-based extractive phase. The FT-IR, 1H 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-1, respectively. The calibration plots are linear in the 1-1000, 3-1000, 10-750, and 3-750 μg L-1, respectively. The intra-and inter-day precision at 50 and 200 μg L-1 levels are 2.9-7.1 % and 3.5-8%, while recoveries are between 84 and 111 %.
CONCLUSIONS: 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.