Li Yun, Yang Jiajia, Huang Chaonan, Wang Longxing, Wang Jincheng, Chen Jiping
Key Laboratory of Separation Sciences for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, PR China.
Key Laboratory of Separation Sciences for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, PR China.
J Chromatogr A. 2015 May 1;1392:28-36. doi: 10.1016/j.chroma.2015.03.003. Epub 2015 Mar 9.
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, 314.2 m(2) g(-1); pore size, 7.9 nm; 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 (0.4-4.6 ng mL(-1) detection of limits) and linearity (R(2)>0.990 for 10-2000 ng mL(-1) of KEP and IBU, and 1-200 ng mL(-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 300 ng mL(-1) for KEP and IBU, 3 and 30 ng mL(-1) for NAP) were obtained in the range of 85.7-113.9% with RSD values below 9.3% (n=3).
通过在氨丙基官能化的KIT-6介孔内生长树枝状分支，合成了一种基于大孔三维立方韩国科学技术院-6（KIT-6）的新型树枝状大分子功能化介孔二氧化硅材料。使用透射电子显微镜、氮吸附-脱附测量、傅里叶变换红外（FTIR）光谱和元素分析进行的详细物理表征表明，多功能树枝状大分子已在介孔的受限空间内成功生长。尽管KIT-6的三维有序介孔结构得到了很好的保留，但当树枝状大分子代数增加到六代时，孔径、比表面积（SBET）和孔体积出现了显著且持续的下降。为了在SBET、孔径和功能密度之间取得折衷，选择了第二代树枝状大分子功能化的KIT-6（DF-KIT-6）（SBET，314.2 m² g⁻¹；孔径，7.9 nm；碳和氮含量，19.80%和1.92%）用于固相萃取（SPE）应用。由于树枝状大分子同时含有烃类和胺类官能团，因此将DF-KIT-6评估为用于萃取所选酸性药物（酮洛芬，KEP；萘普生，NAP；布洛芬，IBU）的反相/阴离子交换混合模式吸附剂。对萃取效率的有效参数，如样品pH值和体积、洗脱剂和洗涤溶剂的类型和体积进行了优化。在优化的实验条件下，基于DF-KIT-6的SPE与HPLC-UV方法相结合，表现出良好的灵敏度（检测限为0.4 - 4.6 ng mL⁻¹）和线性（对于10 - 2000 ng mL⁻¹的KEP和IBU以及1 - 200 ng mL⁻¹的NAP，R²>0.990）。还证明了DF-KIT-6吸附剂在人尿液样品中对酸性药物进行预浓缩和净化的潜在用途。在两个加标水平（KEP和IBU为30和300 ng mL⁻¹，NAP为3和30 ng mL⁻¹）下获得了令人满意的回收率，范围为85.7 - 113.9%，相对标准偏差值低于9.3%（n = 3）。
