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Dendrimer-functionalized mesoporous silica as a reversed-phase/anion-exchange mixed-mode sorbent for solid phase extraction of acid drugs in human urine A

Li, Yun, Yang, Jiajia, Huang, Chaonan, Wang, Longxing, Wang, Jincheng, Chen, Jiping
Journal of chromatography 2015 v.1392 pp. 28-36
Fourier transform infrared spectroscopy, carbon, dendrimers, dendrites, high performance liquid chromatography, ibuprofen, ketoprofen, nitrogen, nitrogen content, pH, porosity, porous media, silica, solid phase extraction, solvents, sorbents, surface area, transmission electron microscopy, urine, Korean Peninsula
A new dendrimer-functionalized mesoporous silica material based on large-pore 3D cubic Korea Advanced Institute of Science and Technology-6 (KIT-6) was synthesized by the growing of dendritic branches inside the mesopores of aminopropyl functionalized KIT-6. Detailed physical characterizations using transmission electron microscopy, nitrogen adsorption–desorption measurements, Fourier transform infrared (FTIR) spectroscopy, and elemental analysis reveal that the multifunctional dendrimers have been grown successfully within the confined spaces of mesopores. Although the 3D ordered mesoporous architecture of KIT-6 was well preserved, there was a significant and continuous decrease in pore size, specific surface area (SBET) and pore volume when increasing dendrimer generation up to six. In order to get a compromise between the SBET, pore size and density of functionalities, the dendrimer-functionalized KIT-6 (DF-KIT-6) for generation 2 (SBET, 314.2m²g⁻¹; pore size, 7.9nm; carbon and nitrogen contents, 19.80% and 1.92%) was selected for solid phase extraction (SPE) applications. The DF-KIT-6 was then evaluated as a reversed-phase/anion-exchange mixed-mode sorbent for extraction of the selected acidic drugs (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBU), since the dendrimers contained both hydrocarbonaceous and amine functionalities. The effective parameters on extraction efficiency such as sample pH and volume, type and volume of eluent and wash solvents were optimized. Under the optimized experimental conditions, the DF-KIT-6 based SPE coupled with HPLC-UV method demonstrated good sensitivity (0.4–4.6ngmL⁻¹ detection of limits) and linearity (R²>0.990 for 10–2000ngmL⁻¹ of KEP and IBU, and 1–200ngmL⁻¹ of NAP). The potential use of DF-KIT-6 sorbent for preconcentration and cleanup of acid drugs in human urine samples was also demonstrated. Satisfactory recoveries at two spiking levels (30 and 300ngmL⁻¹ for KEP and IBU, 3 and 30ngmL⁻¹ for NAP) were obtained in the range of 85.7–113.9% with RSD values below 9.3% (n=3).